Group 6 transition metal-containing compositions for vapor deposition of group 6 transition metal-containing films

ABSTRACT

Disclosed are Group 6 transition metal-containing thin film forming precursors to deposit Group 6 transition metal-containing films on one or more substrates via vapor deposition processes.

CROSS REFERENCE TO RELATED APPLICATIONS

This is a divisional application of U.S. patent application Ser. No.15/994,961, filed May 1 2018, the entire contents of which areincorporated herein by reference.

TECHNICAL FIELD

Disclosed are Group 6 transition metal-containing thin film formingcompositions to deposit Group 6 transition metal-containing films on oneor more substrates via vapor deposition processes.

BACKGROUND

Molybdenum and tungsten finds many different applications in thefabrication of nano-devices.

Vapor deposition of Mo, MoO, MoN, and MOS films from MoO₂Cl₂ and/orMoOCl₄ has been reported. See, e.g., U.S. Pat. App. Pub. No. 2017/062224to Applied Materials, Inc.; U.S. Pat. No. 6,416,890 to Glaverbel; U.S.Pat. App. Pub. No. 2018/019165 to Entegris, Inc.; Gesheva et al., SolarEnergy Materials, 3, 1980, 415-424; Shinde et al., NPG Asia Materials2018 10, e468; Hillman et al., Mater Res Bull. 16, 1981, 1345-1359;Chain et al., Thin Solid Films, 1985 123, 3, 197-211; U.S. Pat. App.Pub. No, 2014/023907 to NthDegree Technologies Worldwide, Inc.; and GBPat App Pub No 2548628 to Oxford University Innovation Limited.

Mo containing films, such as Mo₃Si or MoSi₂, were deposited onto Sisubstrates using MO₂Cl₂ by means of CVD at temperatures above 600°C.—Journal of Electrochemical Society (1967), 114(2), 201-4.

Vapor deposition of W, WO, WN, and WS films from WO₂Cl₂ and/or WOCl₄ hasbeen reported. See, e.g., GB Pat App Pub No 2548628 to Oxford UniversityInnovation Limited; U.S. Pat. No. 7,959,891 to Yeda Research &Development Company Ltd, et al.; JP Pat App Pub No 2006/028572 to UlvacJapan, Ltd.; Boran et at, Jilin Daxue Ziran Kexue Xuebao, 1996, 3,49-52; and JP Pat No 102942956 to Applied Materials, Inc.

The MoO₂Cl₂, MoOCl₄, WO₂Cl₂, and/or WOCl₄ precursors are solid at roomtemperature and atmospheric pressure. The difficulties of performingvapor deposition from solid precursors is well known. See, e.g., U.S.Pat. No, 6,984,415 to McFeely et al. and PCT Pub No. WO2012/168924 toL'Air Liquide, Societe Anonyme pour l'Etude et l'Exploitation desProcedes Georges Claude.

Synthesis and characterization of adducts of Mo and W halides andoxyhalides have been reported. See, e.g., Oliveira et al., DaltonTrans., 2015, 44, 14139-14148; Brown et al., Dalton Trans., 2004, 0,2487-2491; Ku{umlaut over ( )}hn et al., Journal of OrganometallicChemistry 1999, 583, 3-10; Al-Ajlouni et al., Eur. J. Inorg. Chem. 2005,1716-1723; Larson et al., Inorganic Chemistry, 1966, 5, 5, 801-805;Master Thesis Jale ÖCAL, 2009, Reactions of oxomolybdenium compoundswith N donor ligands and related computational calculations; Krauss etal., Chem. Berich., 1961, 94, 2864-2876; Marchetti et al., DaltonTrans., 2013, 42, 2477; Kamenar et al., Inorganica Chimica Acta. 65,1982, L245-L247; Arnaiz et al., Polyhedron, 1994, 13. 19, 2745-2749;Barea et al., Inorg. Chem. 1998, 37, 3321-3325; and Davis et al., Eur.J. Inorg. Chem., 2007, 1903-1910.

A need remains for developing Group 6 precursor molecules suitable forvapor phase deposition with controlled thickness and composition at hightemperature.

SUMMARY

Group 6 transition metal-containing film forming compositions aredisclosed. The Group 6 transition metal-containing film formingcompositions comprise a precursor having the formula MEE′XX′,MEXX′X″X′″, MEE′XX′.L_(n), or MEXX′X″X′″.L, wherein M=Mo or W; E=O or S;X═Cl, Br, or I; L is an adduct; and n=1 or 2. The disclosed Group 6transition metal-containing film forming compositions may include on ormore of the following aspects:

-   -   the precursor having the formula MEE′XX′;    -   the precursor being Mo(═O)₂Cl₂;    -   the precursor being Mo(═S)₂Cl₂;    -   the precursor being Mo(═O)(═S)Cl₂;    -   the precursor being W(═O)₂Cl₂;    -   the precursor being W(═S)₂Cl₂;    -   the precursor being W(═O)(═S)Cl₂;    -   the precursor being Mo(═O)₂Br₂;    -   the precursor being Mo(═S)₂Br₂;    -   the precursor being Mo(═O)(═S)Br₂;    -   the precursor being W(═O)₂Br₂;    -   the precursor being W(═S)₂Br₂;    -   the precursor being W(═O)(═S)Br₂;    -   the precursor being Mo(═O)₂I₂;    -   the precursor being Mo(═S)₂I₂;    -   the precursor being Mo(═O)(═S)I₂;    -   the precursor being W(═O)₂I₂;    -   the precursor being W(═S)₂I₂;    -   the precursor being W(═O)(═S)I₂;    -   the composition comprising between approximately 0% w/w and 5%        w/w of MEE′XHX′H;    -   the composition comprising between approximately 0% w/w and 5%        w/w of MO₂(HCl)₂;    -   the precursor having the formula MEEXX′X″X′″;    -   the precursor being Mo(═O)Cl₄;    -   the precursor being Mo(═S)Cl₄;    -   the precursor being W(═O)Cl₄;    -   the precursor being W(═S)Cl₄;    -   the precursor being Mo(═O)Br₄;    -   the precursor being Mo(═S)Br₄;    -   the precursor being W(═O)Br₄;    -   the precursor being W(═S)Br₄;    -   the precursor being Mo(═O)I₄,    -   the precursor being Mo(═S)I₄;    -   the precursor being W(═O)I₄;    -   the precursor being W(═S)I₄;    -   the precursor having the formula MEE′XX′.L_(n);    -   L being selected from the group consisting of ketones        (R—C(═O)—R), amides (R—C(═O)—NR₂), diamides        (R₂N—C(O)—CH₂—C(O)—NR₂), nitriles (R−C≡N), isonitriles (RN═C),        sulfides (R₂S), sulfoxides (R₂SO), esters (R—C(═O)—OR),        di-esters (R—O—C(═O)—CH₂—C(═O)—O—R), ether (R—O—R), polyether        (R—O)_(n), amines (NR₃), or anhydrides (R—C(═O)—O—C(═O)—R), with        each R independently H or a C1-C10 hydrocarbon and n=1-10;    -   L being selected from the group consisting of ketones        (R—C(═O)—R), diamides (R₂N—C(O)—CH₂—C(O)—NR₂), formamide        (H—C(O)—NR₂), acetamide (Me-C(O)—NR₂), nitriles (R—C≡N),        sulfides (R₂S), esters (R—C(═O)—OR), di-ester        (R—O—C(═O)—CH₂—C(═O)—O—R), ether (R—O—R), polyether (R—O)_(n),        or anhydrides (R—C(═O)—O—C(═O)—R), with each R independently H        or a C1-C10 hydrocarbon and n=1-10;    -   L not being tetrahydrofuran (THF), tetramethyletheylenediamine        (TMEDA), or digylme;    -   each R independently being H or a C1-C4 hydrocarbon;    -   each R independently being H or a C5-C10 hydrocarbon;    -   each R independently being H or a linear C5-C10 hydrocarbon;    -   L being a nitrile;    -   the precursor being MoO₂Cl₂.(tBuCN);    -   the precursor being MoO₂Cl₂.(tBuCN)₂;    -   the precursor being MoO₂Cl₂.(nPrCN);    -   the precursor being MoO₂Cl₂.(nPrCN)₂;    -   the precursor being MoO₂Cl₂.(nC₅H₁₁C—CN);    -   the precursor being MoO₂Cl₂.(nC₅H₁₁C—CN)₂;    -   the precursor being MoO₂Cl₂.(iBuCN);    -   the precursor being MoO₂Cl₂.(iBuCN)₂;    -   the precursor being MoO₂Cl₂.(iPrCN);    -   the precursor being MoO₂Cl₂.(iPrCN)₂;    -   L being an anhydride;    -   the precursor being MoO₂Cl₂.(Valeric Anhydride);    -   L being a formamide;    -   the precursor being MoO₂Cl₂.(H—C(═O)—N^(n)Bu₂);    -   the precursor being MoO₂Cl₂.(H—C(═O)—N^(n)Bu₂)₂;    -   the precursor being MoO₂Cl₂.(H—C(═O)—NEt₂);    -   the precursor being MoO₂Cl₂.(H—C(═O)—NEt₂)₂;    -   L being an acetamide;    -   the precursor being MoO₂Cl₂.(Me-C(═O)—NEt₂);    -   the precursor being MoO₂Cl₂.(Me-C(═O)—NEt₂)₂;    -   L being a diamide;    -   the precursor being MoO₂Cl₂.(tetrapropylmalonamide);    -   L being a ketone;    -   the precursor being MoO₂Cl₂.(CH₃C(O)C₄H₉);    -   the precursor being MoO₂Cl₂.(CH₃C(O)C₄H₉)₂;    -   L being an ester (R—CO—OR);    -   the precursor being MoO₂Cl₂.(methyl hexanoate);    -   the precursor being MoO₂Cl₂.(methyl hexanoate)₂;    -   the precursor being MoO₂Cl₂.(amyl acetate);    -   the precursor being MoO₂Cl₂.(amyl acetate)₂;    -   the precursor being MoO₂Cl₂.(methyl valerate);    -   the precursor being MoO₂Cl₂.(methyl valerate)₂;    -   the precursor being MoO₂Cl₂.(ethyl butyrate);    -   the precursor being MoO₂Cl₂.(ethyl butyrate)₂;    -   the precursor being MoO₂Cl₂.(isobutyl isobutyrate);    -   the precursor being MoO₂Cl₂.(isobutyl isobutyrate)₂;    -   the precursor being MoO₂Cl₂.(methyl heptanoate);    -   the precursor being MoO₂Cl₂.(methyl heptanoate)₂;    -   the precursor being MoO₂Cl₂.(isoamyl acetate);    -   the precursor being MoO₂Cl₂.(isoamyl acetate)₂;    -   the precursor being MoO₂Cl₂.(ethyl isovalerate);    -   the precursor being MoO₂Cl₂.(ethyl isovalerate)₂;    -   the precursor being MoO₂Cl₂.(ethyl 2-methylvalerate);    -   the precursor being MoO₂Cl₂.(ethyl 2-methylvalerate)₂;    -   the precursor being MoO₂Cl₂.(isobutyl isovalerate);    -   the precursor being MoO₂Cl₂.(isobutyl isovalerate)₂;    -   the precursor being MoO₂Cl₂.(methyl isovalerate);    -   the precursor being MoO₂Cl₂.(methyl isovalerate)₂;    -   the precursor being MoO₂Cl₂.(sec-butyl butyrate);    -   the precursor being MoO₂Cl₂.(sec-butyl butyrate)₂;    -   the precursor being MoO₂Cl₂.(butyl isobutyrate);    -   the precursor being MoO₂Cl₂.(butyl isobutyrate)₂;    -   the precursor being MoO₂Cl₂.(ethyl 2-ethylbutyrate);    -   the precursor being MoO₂Cl₂.(ethyl 2-ethylbutyrate)₂;    -   the precursor being MoO₂Cl₂.(ethyl valerate);    -   the precursor being MoO₂Cl₂.(ethyl valerate)₂;    -   the precursor being MoO₂Cl₂.(propyl butyrate);    -   the precursor being MoO₂Cl₂.(propyl butyrate)₂;    -   the precursor being MoO₂Cl₂.(methyl butyrate);    -   the precursor being MoO₂Cl₂.(methyl butyrate)₂;    -   the precursor being MoO₂Cl₂.(cyclohexyl butyrate);    -   the precursor being MoO₂Cl₂.(cyclohexyl butyrate)₂;    -   the precursor being MoO₂Cl₂.(ethyl heptanoate);    -   the precursor being MoO₂Cl₂.(ethyl heptanoate)₂;    -   the precursor being MoO₂Cl₂.(ethyl isobutyrate);    -   the precursor being MoO₂Cl₂.(ethyl isobutyrate)₂;    -   the precursor being MoO₂Cl₂.(tert-butyl acetate);    -   the precursor being MoO₂Cl₂.(tert-butyl acetate)₂;    -   the precursor being MoO₂Cl₂.(ethyl tert-butylacetate);    -   the precursor being MoO₂Cl₂.(ethyl tert-butylacetate)₂;    -   the precursor being MoO₂Cl₂.(2-ethyl butylacetate);    -   the precursor being MoO₂Cl₂.(2-ethyl butylacetate)₂;    -   the precursor being MoO₂Cl₂.(butyl propionate);    -   the precursor being MoO₂Cl₂.(butyl propionate)₂;    -   the precursor being MoO₂Cl₂.(tert-butyl propionate);    -   the precursor being MoO₂Cl₂.(tert-butyl propionate)₂;    -   the precursor being MoO₂Cl₂.(cyclohexyl propionate);    -   the precursor being MoO₂Cl₂.(cyclohexyl propionate)₂;    -   the precursor being MoO₂Cl₂.(ethyl 2-chloropropionate),    -   the precursor being MoO₂Cl₂.(ethyl 2-chloropropionate)₂;    -   the precursor being MoO₂Cl₂.(ethyl 3-chloropropionate);    -   the precursor being MoO₂Cl₂.(ethyl 3-chloropropionate)₂;    -   L being a di-ester;    -   the precursor being MoO₂Cl₂.(dibutyl malonate);    -   the precursor being MoO₂Cl₂.(diethyl methylmalonate);    -   the precursor being MoO₂Cl₂.(dipropyl malonate);    -   L being an ether;    -   the precursor being MoO₂Cl₂.(Et₂O);    -   the precursor being MoO₂Cl₂.(Et₂O)₂;    -   the precursor being MoO₂Cl₂.(Bu₂O);    -   the precursor being MoO₂Cl₂.(Bu₂O)₂;    -   L being a polyether;    -   the precursor being MoO₂Cl₂(^(n)Bu-O—CH₂—CH₂—O-^(n)Bu);    -   the precursor being MoO₂Cl₂(Et-O—CH₂—CH₂—O-Et);    -   L being a sulfide;    -   the precursor being MoO₂Cl₂.(Pr₂S)₂,    -   the precursor being MoO₂Cl₂.(2-Me-cSC₄H₈)₂;    -   the precursor being MoO₂Cl₂.(Et₂S)₂;    -   the precursor having the formula MEXX′X″X′″.L;    -   the precursor being MoOCl₄.(tBuCN);    -   the precursor being MoOCl₄.(nPrCN);    -   the precursor being MoOCl₄.(nC₅H₁₁C—CN);    -   the precursor being MoOCl₄.(iBuCN);    -   the precursor being MoOCl₄.(iPrCN);    -   the precursor being MoOCl₄.(Valeric Anhydride);    -   the precursor being MoOCl₄.(^(n)Bu-FMD);    -   the precursor being MoOCl₄.(Et-FMD);    -   the precursor being MoOCl₄.(Et Me-amd);    -   the precursor being MoOCl₄.(tetrapropylmalonamide);    -   the precursor being MoOCl₄.(CH₃C(O)C₄H₉);    -   the precursor being MoOCl₄.(methyl hexanoate);    -   the precursor being MoOCl₄.(Et₂O);    -   the precursor being MoOCl₄.(Bu₂O);    -   the precursor being MoOCl₄(^(n)Bu-O—CH₂—CH₂—O-^(n)Bu);    -   the precursor being MoOCl₄(Et-O—CH₂—CH₂—O-Et);    -   the precursor being MoOCl₄.(Pr₂S);    -   the precursor being MoOCl₄.(2-Me-cSC₄H₈);    -   the precursor being MoOCl₄.(Et₂S).

Also disclosed are Group 6 transition metal-containing film formingcomposition delivery devices comprising a canister having an inletconduit and an outlet conduit and containing any of the Group 6transition metal-containing film forming compositions disclosed above.The disclosed delivery devices may include one or more of the followingaspects:

-   -   an end of the inlet conduit located above a surface of the Group        6 transition metal-containing film forming composition and an        end of the outlet conduit located above the surface of the Group        6 transition metal-containing film forming compositions;    -   an end of the inlet conduit located above a surface of the Group        6 transition metal-containing film forming composition and an        end of the outlet conduit located below the surface of the Group        6 transition metal-containing film forming composition;    -   an end of the inlet conduit located below a surface of the Group        6 transition metal-containing film forming composition and an        end of the outlet conduit located above the surface of the Group        6 transition metal-containing film forming compositions.

Processes are also disclosed for the deposition of Group 6 transitionmetal-containing films on one or more substrates using any of the Group6 transition metal-containing film forming compositions disclosed above.At least one Group 6 transition metal-containing thin film formingcompositions is introduced into a reactor having at least one substratedisposed therein. At least part of the precursor is deposited onto theat least one substrate to form the Group 6 transition metal-containingfilm. The disclosed processes may further include one or more of thefollowing aspects:

-   -   introducing at least one reactant into the reactor;    -   the reactant being plasma-treated;    -   the reactant being remote plasma-treated;    -   the reactant not being plasma-treated;    -   the reactant being selected from the group consisting of H₂,        H₂CO, N₂H₄, NH₃, SiH₄, Si₂H₆, Si₃H₈, SiH₂Me₂, SiH₂Et₂, SiHEt₃,        N(SiH₃)₃, GeH₄, GeH₂Et₂, GeHEt₃, B₂H₆, B(Me)₃, B(Et)₃, hydrogen        radicals thereof, and mixtures thereof;    -   the reactant being H₂;    -   the reactant being NH₃, primary amines, secondary amines,        diamines (ethylene diamine, N-substituted ethylene diamines),        hydrazine, substituted hydrazines, or mixtures thereof;    -   the reactant being a sulfur- or selenide-containing reactant,        such as H₂S, H₂Se, dialkylsulfide, dialkylselenide,        bis(trialkylsilyl)sulfide, bis(trialkylsilyl)selenide, or        combinations thereof;    -   the reactant being selected from the group consisting of: O₂,        O₃, H₂O, H₂O₂, NO, N₂O, NO₂, carboxylic acids, radicals thereof,        and mixtures thereof;    -   the reactant being H₂O;    -   the reactant being plasma treated O₂;    -   the reactant being O₃;    -   the Group 6 transition metal-containing composition and the        reactant being introduced into the reactor simultaneously;    -   the reactor being configured for chemical vapor deposition;    -   the reactor being configured for plasma enhanced chemical vapor        deposition;    -   the Group 6 transition metal-containing composition and the        reactant being introduced into the chamber sequentially;    -   the reactor being configured for atomic layer deposition;    -   the reactor being configured for plasma enhanced atomic layer        deposition;    -   the reactor being configured for spatial atomic layer        deposition;    -   the Group 6 transition metal-containing film being a pure Group        6 transition metal thin film;    -   the Group 6 transition metal-containing film being Mo or W;    -   the Group 6 transition metal-containing film being a Group 6        transition metal silicide or germanide (M_(k)Si_(l) or        M_(k)Ge_(l), wherein M is the Group 6 transition metal and each        of k and l is an integer which inclusively range from 1 to 6);    -   the Group 6 transition metal-containing film being Mo₃Si or        MoSi₂;    -   the Group 6 transition metal-containing film being a Group 6        transition metal oxide (M_(n)O_(m), wherein M is the Group 6        transition metal and each of n and m is an integer which        inclusively range from 1 to 6);    -   the Group 6 transition metal-containing film being MoO₂, MoO₃,        W₂O₃, WO₂, WO₃, W₂O₅;    -   the Group 6 transition metal-containing film being a Group 6        transition metal nitride (M_(o)N_(p), wherein M is the Group 6        transition metal and each of o and p is an integer which        inclusively range from 1 to 6);    -   the Group 6 transition metal-containing film being Mo₂N, MoN,        MoN₂, W₂N, WN, WN₂;    -   the Group 6 transition metal-containing film being a Group 6        transition metal oxy-nitride (M_(q)O_(r)N_(s) wherein M is the        Group 6 transition metal and each of q, r and s is an integer        which inclusively range from 1 to 10);    -   the Group 6 transition metal-containing film being MoON, MoO₂N,        MoON₂, Mo₂ON, WON, WO₂N, WON₂, W₂ON;    -   the Group 6 transition metal-containing film being a tungsten or        molybdenum dichalcogenide such as MoS₂, WS₂, MoSe₂, WSe₂, or        combinations thereof.

Notation and Nomenclature

Certain abbreviations, symbols, and terms are used throughout thefollowing description and claims, and include:

As used herein, the indefinite article “a” or “an” means one or more.

As used herein, the terms “approximately” or “about” mean±10% of thevalue stated.

As used herein, the term “comprising” is inclusive or open-ended anddoes not exclude additional, unrecited materials or method steps; theterm “consisting essentially of” limits the scope of a claim to thespecified materials or steps and additional materials or steps that donot materially affect the basic and novel characteristics of the claimedinvention; and the term “consisting of” excludes any additionalmaterials or method steps not specified in the claim.

As used herein, the chemical formulae containing the doubly-bonded O andS molecules may or may not include the “=” depiction of the double bond.More particularly, one of ordinary skill in the art will recognize thatMEE′XX′ or MEXX′X″X′″ may also be shown as M(=E)(=E′)XX′ orM(=E)XX′X″X′″. Similarly, MoO₂Cl₂, WO₂Cl₂, MoOCl₄, WOCl₄, MoS₂Cl₂,WS₂Cl₂, MoSCl₄, WSCl₄, etc. may also be shown as Mo(═O)₂Cl₂, W(═O)₂Cl₂,Mo(═O)Cl₄, W(═O)Cl₄, Mo(═S)₂Cl₂, W(═S)₂Cl₂, Mo(═S)Cl₄, W(═S)Cl₄, etc.

As used herein, the abbreviation “RT” means room temperature or atemperature ranging from approximately 18° C. to approximately 25° C.

As used herein, the term “adduct” means a molecular entity which isformed by direct combination of two separate molecule entities in such away there is connectivity but no loss of atoms.

As used herein, the abbreviation “EDA” refers to the ethylene diamineadduct and/or reactant (i.e., H₂N—C₂H₄—NH₂); “TFH” refers totetrahydrofuran; “DMF” refers to dimethylformamide.

As used herein, the terms “vaporization,” “sublimation” and“evaporation” are used interchangeably to refer to the general formationof a vapor (gas) from a solid or liquid precursor, regardless of whetherthe transformation is, for example, from solid to liquid to gas, solidto gas, or liquid to gas.

As used herein, the term “anhydrous” means containing betweenapproximately zero ppmv and approximately 100 ppmv moisture andpreferably between approximately zero ppmv and approximately 10 ppmvmoisture.

As used herein, the term “hydrocarbyl group” refers to a functionalgroup containing carbon and hydrogen; the term “alkyl group” refers tosaturated functional groups containing exclusively carbon and hydrogenatoms. The hydrocarbyl group may be saturated or unsaturated. Eitherterm refers to linear, branched, or cyclic groups. Examples of linearalkyl groups include without limitation, methyl groups, ethyl groups,propyl groups, butyl groups, etc. Examples of branched alkyls groupsinclude without limitation, t-butyl. Examples of cyclic alkyl groupsinclude without limitation, cyclopropyl groups, cyclopentyl groups,cyclohexyl groups, etc.

As used herein, the term “aromatic group” refers to cyclic, planarmolecules with a ring of resonance bonds that exhibit more stabilitythan other geometric or connective arrangements with the same set ofatoms. Exemplary aromatic groups include substituted or unsubstitutedphenyl groups (i.e., C₆R₅, wherein each R is independently H or ahydrocarbyl group).

As used herein, the abbreviation “Me” refers to a methyl group; theabbreviation “Et” refers to an ethyl group; the abbreviation “Pr” refersto a propyl group; the abbreviation “nPr” refers to a “normal” or linearpropyl group; the abbreviation “Pr” refers to an isopropyl group; theabbreviation “Bu” refers to a butyl group; the abbreviation “nBu” refersto a “normal” or linear butyl group; the abbreviation “tBu” refers to atert-butyl group, also known as 1,1-dimethylethyl; the abbreviation“sBu” refers to a sec-butyl group, also known as 1-methylpropyl; theabbreviation “iBu” refers to an iso-butyl group, also known as2-methylpropyl; the term “halide” refers to the halogen anions F—, Cl—,Br—, and I—; and the abbreviation “TMS” refers to trimethylsilyl or—SiMe₃.

As used herein, the term “independently” when used in the context ofdescribing R groups should be understood to denote that the subject Rgroup is not only independently selected relative to other R groupsbearing the same or different subscripts or superscripts, but is alsoindependently selected relative to any additional species of that same Rgroup. For example in the formula MR¹ _(x)(NR²R³)_((4-x)), where x is 2or 3, the two or three R¹ groups may, but need not be identical to eachother or to R² or to R³. Further, it should be understood that unlessspecifically stated otherwise, values of R groups are independent ofeach other when used in different formulas.

The standard abbreviations of the elements from the periodic table ofelements are used herein. It should be understood that elements may bereferred to by these abbreviations (e.g., Si refers to silicon, C refersto carbon, H refers to hydrogen, etc.). However, please note that theabbreviation Ar may refer to the inert gas Argon or the chemical moiety2,6-Me₂-C₆H₃ in the chemical formula ArNH(SiMe₃),

Any and all ranges recited herein are inclusive of their endpoints(i.e., x=1 to 4 or x ranges from 1 to 4 includes x=1, x=4, and x=anynumber in between), irrespective of whether the term “inclusively” isused.

BRIEF DESCRIPTION OF THE DRAWINGS

For a further understanding of the nature and objects of the presentinvention, reference should be made to the following detaileddescription, taken in conjunction with the accompanying drawings, inwhich like elements are given the same or analogous reference numbersand wherein:

FIG. 1 is a flowchart of one of the disclosed methods to overcome someof the issues encountered in vapor deposition using solid precursors;

FIG. 2 is a flowchart of one of the disclosed methods to overcome someof the issues encountered in vapor deposition using solid precursors;

FIG. 3 is a flowchart of one of the disclosed methods to overcome someof the issues encountered in vapor deposition using solid precursors;

FIG. 4 is a flowchart of one of the disclosed methods to overcome someof the issues encountered in vapor deposition using solid precursors;

FIG. 5 is a flowchart of one of the disclosed methods to overcome someof the issues encountered in vapor deposition using sold precursors;

FIG. 6 is a block diagram that schematically illustrates an exemplaryALD apparatus;

FIG. 7 is a ThermoGravimetric Analysis (TGA) graph illustrating thepercentage of weight loss of MoO₂Cl₂.L_(n), wherein L is the specifiednitrile and n is 1 or 2, upon temperature increase;

FIG. 8 is a TGA graph illustrating the percentage of weight loss ofMoO₂Cl₂.L_(n), wherein L is dibutylformamide, diethylformamide,2-hexanone, methyl hexanoate, or amyl acetate, and n is 1 or 2, upontemperature increase;

FIG. 9 is a TGA graph illustrating the percentage of weight loss ofMoO₂Cl₂.L_(n), wherein L is diethy ether, dibutyl ether, ethylene glycoldibutyl ether, ethylene glycol diethyl ether, or diglyme, and n is 1 or2, upon temperature increase;

FIG. 10 is a TGA graph illustrating the percentage of weight loss ofMoO₂Cl₂.L_(n), wherein L is diethy sulfide or dipropyl sulfide, and n is1 or 2, upon temperature increase;

FIG. 11 is the ¹H NMR spectrum of the MoO₂Cl₂.(Methyl Hexanoate)₂precursor.

FIG. 12 is the ¹H NMR spectrum of the MoO₂Cl₂.(Amyl Acetate)₂ precursor.

FIG. 13 is a TGA/Differential Thermal Analysis (DTA) graph illustratingthe percentage of weight loss (TGA) or the differential temperature(DTA) of MoO₂Cl₂.(THF)₂ upon temperature increase;

FIG. 14 is a TGA graph illustrating the percentage of weight loss ofMoO₂Cl₂.L_(n), wherein L is TMEDA, and n is 1 or 2, upon temperatureincrease;

FIG. 15 is a TGA/DTA graph illustrating the percentage of weight loss(TGA solid line) or the differential temperature (DTA dotted line) ofMoO₂Cl₂.(heptyl cyanide)₂ upon temperature increase;

FIG. 16 is a graph of the growth rates of the Mo containing film in ALDmode using Mo(═O)₂Cl₂ as a function of the temperature;

FIG. 17 is a graph of the growth rates of the Mo containing film in ALDmode using the Mo(═O)₂Cl₂ as a function of the precursor introductiontime at 400° C.;

FIG. 18 is a graph of the growth rates of the Mo containing film in ALDmode using the Mo(═O)₂Cl₂ as a function of the ammonia introduction timeat 400° C.;

FIG. 19 is a graph of the growth rates of the Mo containing film in ALDmode using the Mo(═O)₂Cl₂ as a function of the number of ALD cycle;

FIG. 20 is an Auger Electron Spectroscopy (AES) graph showing the atomiccomposition of a MoN film deposited at 400° C. as a function of sputtertime;

FIG. 21 is an AES graph showing the atomic composition of a MoN filmdeposited at 425° C. as a function of sputter time;

FIG. 22 is an AES graph showing the atomic composition of a MoN filmdeposited at 450° C. as a function of sputter time;

FIG. 23 is an AES graph showing the atomic composition of a MoN filmdeposited at 475° C. as a function of sputter time;

FIG. 24 is a X-Ray Spectroscopy (XPS) graph of the MoN film produced at400° C. showing the residual amount of chlorine in the film;

FIG. 25 is a graph of the film resistivities as a function oftemperature;

FIG. 26 shows the X-Rays Diffractometry (XRD) analysis of the MoN filmproduced 475° C. showing the characteristic signals of MolybdenumNitride;

FIG. 27 is a Scanning Electron Microscope (SEM) picture of the filmdeposited in a 1:10 aspect ratio pattern wafer at 475° C. and showsnearly perfect step coverage performance;

FIG. 28 is a side view of one embodiment of a liquid Group 6 transitionmetal-containing film forming compositions delivery device 1;

FIG. 29 is a side view of a second embodiment of the Group 6 transitionmetal-containing film forming compositions delivery device 1;

FIG. 30 is an exemplary embodiment of a solid precursor sublimator 100for subliming solid Group 6 transition metal-containing film formingcompositions.

DESCRIPTION OF PREFERRED EMBODIMENTS

Group 6 transition metal-containing film forming compositions aredisclosed. Also disclosed are methods of using the same to form Group 6transition metal-containing films on one or more substrates. Thedisclosed Group 6 transition metal-containing film forming compositionscomprise a Group 6 transition metal containing precursor having theformula MEE′XX′ or MEXX′X″X′″, wherein M=Mo or W; E=O or S; and X═Cl,Br, or I. In another alternative, the Group 6 transition metalcontaining precursor may be a MEE′XX′.L_(n) adduct, wherein M=Mo or W,E=O or S; X═Cl, Br, or I; L is an ligand; and n=1 or 2, provided L isnot tetrahydrofuran, tetramethylethylenediamine, or diglyme. In anotheralternative, the Group 6 transition metal containing precursor may be aMEXX′X″X′″.L adduct, wherein M=Mo or W; E=O or S; X═Cl, Br, or I; and Lis an ligand.

L may be selected from ketones (R—C(═O)—R), amides (R—C(═O)—NR₂),diamides (R₂N—C(O)—CH₂—C(O)—NR₂), nitriles isonitriles (RN═C), sulfides(R₂S), sulfoxides (R₂SO), esters (R—C(═O)—OR), di-esters(R—O—C(═O)—CH₂—C(═O)—O—R), ether (R—O—R), polyether (R—O)_(n), amines(NR₃), or anhydrides (R—C(═O)—O—C(═O)—R), with each R independently H ora C1-C10 hydrocarbon and n=1-10. Adjacent Rs may form a cyclic structure(e.g., NR2 may be pyridine, pyrrole, etc). One or more Rs may beselected from H or a C1-C4 hydrocarbon to produce a more volatileligand, Alternatively, one or more Rs may be selected from a C5-C10hydrocarbon to produce a less volatile ligand. In another alternative,one or more Rs that are linear C5-C10 hydrocarbon may help produceliquid precursors. Any combination of these alternative may bejudicially selected to produce a precursor with the desired stabilityand volatility.

For MEE′XX′.L is preferably selected from the group consisting ofketones (R—C(═O)—R), diamides (R₂N—C(O)—CH₂—C(O)—NR₂), formamide(H—C(O)—NR₂), acetamide (Me-C(O)—NR₂), nitriles (R—C≡N), sulfides (R₂S),esters (R—C(═O)—OR), ether (R—O—R), polyether (R—O)_(n), and anhydrides(R—C(═O)—O—C(═O)—R).

These precursors must be handled under anhydrous conditions to avoidformation of any hydrated by-products, such as MEE′HXHX′. As a result,the Group 6 transition metal-containing film forming compositioncontains between approximately 0% w/w and 5% w/w of any MEE′HXHX′by-products, such as MoO₂(HCl)₂ as determined by X-Ray Diffraction(XRD). The presence of any hydrated by-products may form HCl and H₂Oupon heating. If the disclosed precursors are not handled inmoisture-free conditions, the by-products may form a crust on thesurface of the precursors that prevents its sublimation.

Exemplary Mo-containing MEE′XX′ precursors include Mo(═O)₂Cl₂,Mo(═S)₂Cl₂, Mo(═O)(═S)Cl₂, Mo(═O)₂Br₂, Mo(═S)₂Br₂, Mo(═O)(═S)Br₂,Mo(═O)₂I₂, Mo(═S)₂I₂, or Mo(═O)(═S)I₂. These precursors may beinteresting when the underlying film may be damaged by anyhalogen-containing by-products. The larger halide containing precursors(i.e., Br or I) may further be less damaging than the Cl containingprecursors. The halide-metal is also weaker for larger halides, thusenabling reduction based deposition processes at a lower temperaturethan with Cl.

Exemplary Mo-containing MEXX′X″X′″ precursors include Mo(═O)Cl₄,Mo(═S)Cl₄, Mo(═O)Br₄, Mo(═S)Br₄, Mo(═O)I₄, or Mo(═S)I₄. These precursorsmay be interesting when little to no oxygen is desired in the resultingfilm.

Exemplary W-containing MEE′XX″ precursors include W(═O)₂Cl₂ W(═S)₂Cl₂;W(═O)(═S)Cl₂, W(═O)₂Br₂, W(═S)₂Br₂, W(═O)(═S)Br₂, W(═O)₂I₂, W(═S)₂I₂, orW(═O)(═S)I₂. These precursors may be interesting when the underlyingfilm may be damaged by any halogen-containing by-products. The largerhalide containing precursors (i.e., Br or I) may further be lessdamaging than the Cl containing precursors.

Exemplary W-containing MEXX′X″X′″ precursors include W(═O)Cl₄, W(═S)Cl₄,W(═O)Br₄, W(═S)Br₄, W(═O)I₄, or W(═S)I₄. These precursors may beinteresting when little to no oxygen is desired in the resulting film.

Exemplary nitrile adducts include pivalonitrile (tBuCN), butyronitrile(nPrCN), hexanenitrile (nC₅H₁₁—CN), isovaleronitrile (iBuCN), orisobutyronitrile (iPrCN).

For example, the Mo— and nitrile-containing MEE′XX′(L)_(n) precursor maybe MoO₂Cl₂.(tBuCN), MoO₂Cl₂.(tBuCN)₂, MoO₂Cl₂.(nPrCN), MoO₂Cl₂.(nPrCN)₂,MoO₂Cl₂.(nC₅H₁₁C—CN), MoO₂Cl₂.(nC₅H₁₁C—CN)₂, MoO₂Cl₂.(iBuCN),MoO₂Cl₂.(iBuCN)₂, MoO₂Cl₂.(iPrCN), or MoO₂Cl₂.(iPrCN)₂.

Alternatively, the W— and nitrile-containing MEE′XX′(L)_(n), precursormay be WO₂Cl₂.(tBuCN), WO₂Cl₂.(tBuCN), WO₂Cl₂.(tBuCN)₂, WO₂Cl₂.(nPrCN),WO₂Cl₂.(nPrCN)₂, WO₂Cl₂.(nC₅H₁₁C—CN), WO₂Cl₂.(nC₅H₁₁C—CN)₂,WO₂Cl₂.(iBuCN), WO₂Cl₂.(iBuCN)₂, WO₂Cl₂.(iPrCN), and WO₂Cl₂.(iPrCN)₂.

In another alternative, the Mo— and nitrile-containing MEXX′X″X′″(L)_(n)precursor may be MoOCl₄.(tBuCN), MoOCl₄.(nPrCN), MoOCl₄.(nC₅H₁₁C—CN),MoOCl₄.(iBuCN), and MoOCl₄.(iPrCN).

In yet another alternative, the W— and nitrile containingMEXX′X″X′′(L)_(n) precursor may be WOCl₄. (tBuCN), WOCl₄.(nPrCN),WOCl₄.(nC₅H₁₁C—CN), WOCl₄.(iBuCN), and WOCl₄.(iPrCN).

As shown in the examples that follow, MoO₂Cl₂(nC₅H₁₁—CN) is particularlypromising for vapor deposition technologies because it is aclear/yellowish, low temperature melting solid (approximately 38° C.).Additionally, MoO₂Cl₂(nC₅H₁₁—CN) has a vapor pressure of approximately 8torr at approximately 100° C.

Exemplary anhydride adducts include valeric anhydride (VA). For example,the VA precursor may be MoO₂Cl₂.(VA), WO₂Cl₂.(VA), MoOCl₄.(VA), orWOCl₄.(VA).

Exemplary amide adducts include formamide adducts, such asN,N-dibutylformamide (H—C(O)—NBu₂) and N,N-diethylformamide(H—C(O)—NEt₂), and acetamide adducts, such as N,N-diethylacetamide(Me-C(O)—NEt₂). For example, the amide precursor may beMoO₂Cl₂.(H—C(═O)—N^(n)Bu₂)₂, MoO₂Cl₂.(H—C(═O)—N^(n)Bu₂)₂,MoO₂Cl₂.(H—C(═O)—NEt₂), MoO₂Cl₂.(H—C(═O)—NEt₂)₂,MoO₂Cl₂.(Me-C(═O)—NEt₂), MoO₂Cl₂.(Me-C(═O)—NEt₂)₂,WO₂Cl₂.(H—C(═O)—N^(n)Bu₂)₂, WO₂Cl₂.(H—C(═O)—N^(n)Bu₂)₂,WO₂Cl₂.(H—C(═O)—NEt₂), WO₂Cl₂.(H—C(═O)—NEt₂)₂, WO₂Cl₂.(Me-C(═O)—NEt₂),WO₂Cl₂.(Me-C(═O)—NEt₂)₂, MoOCl₄.(H—C(═O)—N^(n)Bu₂),MoOCl₄.(H—C(═O)—NEt₂), MoOCl₄.(Me-C(═O)—NEt₂), WOCl₄.(H—C(═O)—N^(n)Bu₂),WOCl₄.(H—C(═O)—NEt₂), or WOCl₄.(Me-C(═O)—NEt₂). TheMoO₂Cl₂(H—C(O)—NBu₂)_(n) and MoO₂Cl₂(H—C(O)—NEt₂)_(n) precursors were,however, less volatile than MoO₂Cl₂ with other L adducts.

Exemplary diamide adducts include N,N,N′,N′-tetrapropylmalonamide(TPMA). For example, the diamide precursor may be MoO₂Cl₂.(TPMA),WO₂Cl₂.(TPMA), MoOCl₄.(TPMA), or WOCl₄.(TPMA).

Exemplary ketone adducts include 2-hexanone (CH₃C(O)C₄H₉). For example,the ketone precursor may be MoO₂Cl₂.(CH₃C(O)C₄H₉),MoO₂Cl₂.(CH₃C(O)C₄H₉)₂, WO₂Cl₂.(CH₃C(O)C₄H₉), WO₂Cl₂.(CH₃C(O)C₄H₉)₂,MoOCl₄.(CH₃C(O)C₄H₉), or WOCl₄.(CH₃C(O)C₄H₉).

Exemplary ester adducts include methyl hexanoate (MHX), amyl acetate(AA), methyl valerate (MV), ethyl butyrate (EB), isobutyl isobutyare(IIB), methyl heptanoate (MHP), isoamyl acetate (IA), ethyl isovalerate(EI), ethyl 2-methylvalerate (EMV), isobutyl isovalerate (IIV), methylisovalerate (MI), sec-butyl butyrate (BB), butyl isobutyrate (BIB),ethyl 2-ethylbutyare (EEB), ethyl valerate (EV), propyl butyrate (PB),methyl butyrate (MB), cyclohexyl butyrate (CHB), ethyl heptanoate (EH),ethyl isobutyare (EIB), tert-butyl acetate (TA), ethyl tert-butylacetate(EBA), 2-ethyl butylacetate (2-EBA), butyl propionate (BP), tert-butylpropionate (tBP), cyclohexyl propionate (CHP), ethyl 2-chloropropionate(2-ECP), ethyl 3-chloropropionate (3-ECP), and combinations thereo.

For example, the Mo— and ester-containing precursors includeMoO₂Cl₂.(MHX), MoO₂Cl₂.(MHX)₂, MoO₂Cl₂.(AA), MoO₂Cl₂.(AA)₂,MoO₂Cl₂.(MV), MoO₂Cl₂.(MV)₂, MoO₂Cl₂.(EB), MoO₂Cl₂.(EB)₂, MoO₂Cl₂.(MHP),MoO₂Cl₂.(MHP)₂, MoO₂Cl₂.(IIB), MoO₂Cl₂.(IIB)₂, MoO₂Cl₂.(IA),MoO₂Cl₂.(IA)₂, MoO₂Cl₂.(EI), MoO₂Cl₂.(EI)₂, MoO₂Cl₂.(EMV),MoO₂Cl₂.(EMV)₂, MoO₂Cl₂.(IIV), MoO₂Cl₂.(IIV)₂, MoO₂Cl₂.(MI),MoO₂Cl₂.(MI)₂, MoO₂Cl₂.(BB), MoO₂Cl₂.(BB)₂, MoO₂Cl₂.(BIB),MoO₂Cl₂.(BIB)₂, MoO₂Cl₂.(EEB), MoO₂Cl₂.(EEB)₂, MoO₂Cl₂.(EV),MoO₂Cl₂.(EV)₂, MoO₂Cl₂.(PB), MoO₂Cl₂.(PB)₂, MoO₂Cl₂.(MB), MoO₂Cl₂.(MB)₂,MoO₂Cl₂.(CHB), MoO₂Cl₂.(CHB)₂, MoO₂Cl₂.(EH), MoO₂Cl₂.(EH)₂,MoO₂Cl₂.(EIB), MoO₂Cl₂.(EIB)₂, MoO₂Cl₂.(TA), MoO₂Cl₂.(TA)₂,MoO₂Cl₂.(EBA), MoO₂Cl₂.(EBA)₂, MoO₂Cl₂.(2-EBA), MoO₂Cl₂.(2-EBA)₂,MoO₂Cl₂.(BP), MoO₂Cl₂.(BP)₂, MoO₂Cl₂.(tBP), MoO₂Cl₂.(tBP)₂,MoO₂Cl₂.(CHP), MoO₂Cl₂.(CHP)₂, MoO₂Cl₂.(2-ECP), MoO₂Cl₂.(2-ECP)₂,MoO₂Cl₂.(3-ECP), MoO₂Cl₂.(3-ECP)₂, or combinations thereof.

For example, the W— and ester-containing precursors includeWO₂Cl₂.(MHX), WO₂Cl₂.(MHX)₂, WO₂Cl₂.(AA), WO₂Cl₂.(AA)₂, WO₂Cl₂.(MV),WO₂Cl₂.(MV)₂, WO₂Cl₂.(EB), WO₂Cl₂.(EB)₂, WO₂Cl₂.(MHP), WO₂Cl₂.(MHP)₂,WO₂Cl₂.(IIB), WO₂Cl₂.(IIB)₂, WO₂Cl₂.(IA), WO₂Cl₂.(IA)₂, WO₂Cl₂.(EI),WO₂Cl₂.(EI)₂, WO₂Cl₂.(EMV), WO₂Cl₂.(EMV)₂, WO₂Cl₂.(IIV), WO₂Cl₂.(IIV)₂,WO₂Cl₂.(MI), WO₂Cl₂.(MI)₂, WO₂Cl₂.(BB), WO2Cl₂.(BB)₂, WO₂Cl₂.(BIB),WO₂Cl₂.(BIB)₂, WO₂Cl₂.(EEB), WO₂Cl₂.(EEB)₂, WO₂Cl₂.(EV), WO₂Cl₂.(EV)₂,WO₂Cl₂.(PB), WO₂Cl₂.(PB)₂, WO₂Cl₂.(MB), WO₂Cl₂.(MB)₂, WO₂Cl₂.(CHB),WO₂Cl₂.(CHB)₂, WO₂Cl₂.(EH), WO₂Cl₂.(EH)₂, WO₂Cl₂.(EIB), WO₂Cl₂.(EIB)₂,WO₂Cl₂.(TA), WO₂Cl₂.(TA)₂, WO₂Cl₂.(EBA), WO₂Cl₂.(EBA)₂, WO₂Cl₂.(2-EBA),WO₂Cl₂.(2-EBA)₂, WO₂Cl₂.(BP), WO₂Cl₂.(BP)₂, WO₂Cl₂.(tBP), WO₂Cl₂.(tBP)₂,WO₂Cl₂.(CHP), WO₂Cl₂.(CHP)₂, WO₂Cl₂.(2-ECP), WO₂Cl₂.(2-ECP)₂,WO₂Cl₂.(3-ECP), WO₂Cl₂.(3-ECP)₂, or combinations thereof.

Alternatively, the Mo— and ester-containing precursors includeMoOCl₄.(MHX), MoOCl₄.(AA), MoOCl₄.(MV), MoOCl₄.(EB), MoOCl₄.(MHP),MoOCl₄.(IIB), MoOCl₄.(IA), MoOCl₄.(EI), MoOCl₄.(EMV), MoOCl₄.(IIV),MoOCl₄.(MI), MoOCl₄.(BB), MoOCl₄.(BIB), MoOCl₄.(EEB), MoOCl₄.(EV),MoOCl₄.(PB), MoOCl₄.(MB), MoOCl₄.(CHB), MoOCl₄.(EH), MoOCl₄.(EIB),MoOCl₄.(TA), MoOCl₄.(EBA), MoOCl₄.(2-EBA), MoOCl₄.(BP), MoOCl₄.(tBP),MoOCl₄.(CHP), MoOCl₄.(2-ECP), MoOCl₄.(3-ECP), or combinations thereof.

Alternatively, the W— and ester-containing precursors includeWOCl₄.(MHX), WOCl₄.(AA), WOCl₄.(MV), WOCl₄.(EB), WOCl₄.(MHP),WOCl₄.(IIB), WOCl₄.(IA), WOCl₄.(EI), WOCl₄.(EMV), WOCl₄.(IIV),WOCl₄.(MI), WOCl₄.(BB), WOCl₄.(BIB), WOCl₄.(EEB), WOCl₄.(EV),WOCl₄.(PB), WOCl₄.(MB), WOCl₄.(CHB), WOCl₄.(EH), WOCl₄.(EIB),WOCl₄.(TA), WOCl₄.(EBA), WOCl₄.(2-EBA), WOCl₄.(BP), WOCl₄.(tBP),WOCl₄.(CHP), WOCl₄.(2-ECP), WOCl₄.(3-ECP), or combinations thereof.

As shown in the examples that follow, MoO₂Cl₂.(MH)₂ and MoO₂Cl₂.(AA)₂are particularly promising for vapor deposition technologies becauseboth are a liquid at room temperature and atmospheric pressure.Additionally, MoO₂Cl₂.(MH)₂ has a vapor pressure of approximately 14torr at approximately 100° C. and MoO₂Cl₂.(AA)₂ has a vapor pressure ofapproximately 8.5 torr at approximately 100° C. (as compared toapproximately 24 Torr at 100° C. for MoO₂Cl₂). The vacuumthermogravimetric analysis (TGA) curves also indicate that MoO₂Cl₂.(MH)₂and MoO₂Cl₂.(AA)₂ exhibit the stability needed for vapour depositionprocesses. Applicants were surprised by these results because esters aretypically considered difficult adducts because they weakly bind to themetal and tend to produce leaving groups and active organic moieties.While testing is ongoing and as partially demonstrated in the examplesthat follow, Applicants remain confident that the reaction productbetween MoO₂Cl₂ and the ester is MoO₂Cl₂.L₂ because esters are not proneto accept oxygen from a metal center and contain no H or C═C to acceptCl.

Exemplary di-ester adducts include dibutyl malonate (DBM), diethylmethylmalonate (DEMM), and dipropyl malonate (DPM). For example, thedi-ester precursor may be MoO₂Cl₂.(DBM), MoO₂Cl₂.(DEMM), MoO₂Cl₂.(DPM),WO₂Cl₂.(DBM), WO₂Cl₂.(DEMM), WO₂Cl₂.(DPM), MoOCl₄.(DBM), MoOCl₄.(DEMM),MoOCl₄.(DPM), WOCl₄.(DBM), WOCl₄.(DEMM), or WOCl₄.(DPM).

Exemplary ether adducts include diethyl ether (Et₂O) and dibutyl ether(Bu₂O). For example, the ether precursor may be MoO₂Cl₂.(Et₂O),MoO₂Cl₂.(Et₂O)₂, MoO₂Cl₂.(Bu₂O), MoO₂Cl₂.(Bu₂O)₂, WO₂Cl₂.(Et₂O),WO₂Cl₂.(Et₂O)₂, WO₂Cl₂.(Bu₂O), WO₂Cl₂.(Bu₂O)₂, MoOCl₄.(Et₂O),MoOCl₄.(Bu₂O), WOCl₄.(Et₂O), or WOCl₄.(Bu₂O).

Exemplary polyether adducts include ethylene glycol dibutyl ether(^(n)Bu-O—CH₂—CH₂—O-^(n)Bu or EGBE) and ethylene glycol diethyl ether(Et-O—CH₂—CH₂—O-Et or EGEE), Exemplary polyether precursors includeMoO₂Cl₂.(^(n)Bu-O—CH₂—CH₂—O—^(n)Bu), MoO₂Cl₂(Et-O—CH₂—CH₂—O-Et),WO₂Cl₂(^(n)Bu-O—CH₂—CH₂—O-^(n)Bu), WO₂Cl₂(Et-O—CH₂—CH₂—O-Et),MoOCl₄(^(n)Bu-O—CH₂—CH₂—O-^(n)Bu), MoOCl₄(Et-O—CH₂—CH₂—O-Et),WOCl₄(^(n)Bu-O—CH₂—CH₂—O-^(n)Bu), or WOCl₄(Et-O—CH₂—CH₂—O-Et).

As shown in the examples that follow, MoO₂Cl₂(EGBE) is particularlypromising for vapor deposition technologies because it is a blue oil atroom temperature and atmospheric pressure. Additionally, MoO₂Cl₂(EGBE)remains stable at 120° C. for over 7 hours and exhibits a vapor pressureof approximately 1.9 torr at 120° C. Vacuum TGA of MoO₂Cl₂(EGBE) showeda dean curve with approximately 4% residue.

Exemplary sulfide adducts include dipropyl sulfide (Pr₂S), 2-methyltetrahydrothiophene (2-Me-cSC₄H₈), or diethyl sulfide (Et₂S). Forexample, the sulfide precursors may include MoO₂Cl₂.(Pr₂S)₂,MoO₂Cl₂.(2-Me-cSC₄H₈)₂, MoO₂Cl₂.(Et₂S)₂, WO₂Cl₂.(Pr₂S)₂,WO₂Cl₂.(2-Me-cSC₄H₈)₂, WO₂Cl₂.(Et₂S)₂, MoOCl₄.(Pr₂S),MoOCl₄.(2-Me-cSC₄H₈), MoOCl₄.(Et₂S), WOCl₄.(Pr₂S), WOCl₄.(2-Me-cSC₄H₈),or WOCl₄.(Et₂S).

These precursors are commercially available or may be synthesized bymethods known in the art.

Both MEE′XX′(L)_(n), and MEXX′X″X′″(L) are frequently used as catalysts.For vapor deposition, MoO₂Cl₂ is more volatile and thermally stable thanMoOCl₄. However, based on the results from the ester adducts, Applicantsbelieve that MoO₂Cl₂ is such a good catalyst that it may be reactingwith its adducts. As a result, most of the MoO₂Cl₂.L_(n) precursors maynot improve upon the vapor deposition performance of MoO₂Cl₂ (althoughas discussed herein, there are some surprisingly good MoO₂Cl₂.L_(n)precursors). Additionally, the adducts that work for MoO₂Cl₂ may notwork as well for MoOCl₄. As a result, Applicant expects that theMoOCl₄.L precursors may improve upon the vapor deposition performance ofMoOCl₄.

Although many patent applications and journal articles have beenpublished regarding use of the MEE′XX′ or MEXX′X″X′′ precursors forvapor deposition, commercial implementation currently remains elusivefor a variety of reasons.

For example, any films already deposition on the substrate may be etchedby any halide by-products produced during the deposition process.

Additionally, the MEE′XX′ or MEXX′X″X′″ precursors are solids at ambienttemperature and pressure. Precursors that are solids at ambienttemperature and pressure are typically not industrialized or, if theyare, only for applications requiring small usage due to facilitation andprocess issues. Solid precursors are not preferred when a large volumeof material is needed.

The reproducible and stable production of vapor from solid precursors ischallenging at best. Solid precursors may be dissolved in a solvent andthe solution vaporized, but the solvent may introduce impermissiblecontamination issues into the resulting film. Any solvent utilizedcannot react with the solid precursor. Additionally, the solventsevaporation rate cannot negatively affect the vapor pressure of thesolid material. As disclosed in the file for U.S. Pat. No. 8,435,428 toAir Liquide Electronics U.S. LP, the concentration of the precursor maydecrease during delivery even when the vapor pressure of the solvent andprecursor are nearly identical. As a result, identification of suitablesolvents for solid precursors may be difficult at best.

Alternatively, a sublimator may be used to produce vapors from the solidmaterial directly. However, the volume of vaporized product obtainedfrom sublimated solids remains considerably lower than that of vaporizedliquids. Higher temperatures and longer processing times may also berequired to obtain a sufficient amount of material needed to form thesemiconductor thin film, resulting in the aforementioned facilitationand process issues. For example, any lines from the sublimator to theprocessing equipment may need to be heated to maintain the precursor invapor form. And the temperature required to produce the resulting filmmay be too high and damage the underlying layers on the substrate.Additionally, the particle size distribution of any solid materials mustbe controlled to provide consistent sublimation rates and vapor pressurefrom batch to batch.

The sublimator transfers heat to the solid precursors unevenly, with thesolid material closest to the heating source receiving more heat thansolid material that is located further away from the heating source.This results in uneven heat distribution and therefore uneven vaporpressure. As a result, a large amount of solid precursor cannottypically be filled into the sublimator. Current commercial sublimatorvolumes range from 500 g to 1 kg. As a result, any processes usingsublimated material may require the use of multiple small sublimators.

Maintaining the original solid distribution in the sublimator is alsodifficult. While the solid material may originally be evenly distributedin the sublimator, shipping or even connecting the sublimator to thesemiconductor processing apparatus may jostle the solid materials. Thisalso may negatively affect the sublimator's capability to produce aconsistent and reproducible concentration of the vapor o semiconductorprocess.

Further complicating matters, the density of purified MEE′XX′ orMEXX′X″X′″ precursors may vary. For example, the reported crystaldensity of MoOCl₄, MoO₂Cl₂, WoO₂Cl₂, and WOCl₄ at 25° C. and 1 atmpressure is 2.68 g/mL, 3.31 g/mL, 4.67 g/mL and 4.62 g/mL, respectively.However, sublimation of MoO₂Cl₂ and WOCl₄ may produce materials withvarying bulk densities, including some lightweight materials having verylow bulk density. Bulk density is the mass of the material divided bythe total volume occupied by the material. The total volume may includethe volume of the particles of the solid material, the volume of anyinter-particle voids, and the volume of any internal pores. As a result,the bulk density may vary depending on how the material is handled. Thepurified MEE′XX′ or MEXX′X″X′″ precursors may have a bulk densityranging from approximately 0.3 to approximately 1.5 g/mL and typicallyfrom approximately 0.6 to approximately 1.1 g/mL.

In addition to the solid precursor complications discussed above, theselow bulk density solids may become entrained in the vapor stream.Needless to say, the resulting addition of these low bulk density solidparticulates to thin films is not acceptable in the semiconductorindustry. Additionally, some low bulk density materials may carry anelectrostatic charge. The charged materials are difficult to work withbecause the fly around the work area, including the inside of the glovebox and the surface of any the containers. Additionally, when removedfrom the inert atmosphere, the flakes that escape corrode any corrosivesurfaces to which they adhere.

The difficulty of handling MoO₂Cl₂ is well known. See, e.g., Armarego etal., Purification of Laboratory Chemicals, 2013, ISBN: 0123821614, p,590, stating “Commercial fluffy MoO₂Cl₂ gives poor yields ofsubstitution products (e.g., with ArNHSiMe₃), but the THF complexMoO₂Cl₂.THF₂ is easier to handle, reacts in a similar way, and givesmuch higher yields of substitution products”; and Stock et al., AdvancedSynthesis and Catalysis, Vol. 354, Issue 11-12, page 2309, stating “Incontrast to MoO₂Cl₂, which was a fluffy powder. MoO₂Cl₂.DMF₂ consistedvisibly of crystals. For this reason, a predetermined mg-amount ofMoO₂Cl₂.DMF₂ could be charged into a reaction flask more easily.”

To overcome these challenges, Applicants have developed several methodsto make the MEE′XX′ or MEXX′X″X′″ precursors suitable for use in vapordeposition processes. All of the disclosed processes should be performedunder anhydrous and inert conditions to avoid formation of ME2(OH)₂ andrelease of any corrosive and toxic hydrogen halide gas.

FIG. 1 is a flowchart illustrating one method to overcome some of theissues discussed above. More specifically, the low density MEE′XX′ orMEXX′X″X′″ precursors may be converted to high density MEE′XX′ orMEXX′X″X′″ precursors using temperature, pressure, or both. For a timeranging from approximately 1 minute to approximately 24 hours,preferably from 1 minute to 12 hours, more preferably from 1 hour to 3hours, the MEE′XX′ or MEXX′X″X′″ precursors may be heated to atemperature ranging from approximately 0° C. to approximately 200° C.,preferably from approximately 25° C. to approximately 150° C., and morepreferably from approximately 80° C. to approximately 120° C.Alternatively, for the same time period, the MEE′XX′ or MEXX′X″X′″precursors may be pressurized to a pressure ranging from approximately 1atm to approximately 500 atm, more preferably from approximately 10 toapproximately 200 atm. In another alternative, both the heating andpressurization may be performed simultaneously for the same time period.In another alternative, both the heating and pressurization may beperformed sequentially for all or part of the time period. One ofordinary skill in the art will recognize the equipment needed to performthe heating and pressurization processes.

Applicants have discovered that uneven thermal treatment of the MEE′XX′or MEXX′X″X′″ precursor may produce product having differing densitiesthroughout. More particularly, uneven heating and cooling of MoO₂Cl₂ andWOCl₄ results in both a light, statically-charged flake and a densechunky material. The statically-charged flakes are difficult to workwith because they fly around the work area, including the inside of theglove box and the surface of any the containers. Additionally, whenremoved from the inert atmosphere, the flakes that escape corrode anycorrosive surfaces to which they adhere. Finally, both the light flakeand the dense chunky material still exhibit a low bulk density (e.g.,ranging from approximately 0.3 to approximately 1.5 g/mL and typicallyfrom approximately 0.6 to approximately 1.1 g/mL). As a result, thesublimator contains less material and the customer requires moresublimators for any vapor deposition processes.

To overcome these issues, a pressure-resistant container of the MEE′XX′precursor is sealed and placed into an insulated atmospheric furnace.The pressure-resistant container may be made from any non-corrosivematerials, such as glass, halide resistant stainless steel, PTFE, etc.The furnace may be set to slightly above the melting point of theMEE′XX′ or MEXX′X″X′″ precursor. For MoO₂Cl₂, the furnace is set to atemperature ranging from approximately 185° C. to approximately 205° C.The container may be placed into the furnace before heating or into apre-heated furnace. The container is heated for a time period sufficientto melt the MEE′XX′ or MEXX′X″X′″ precursor. One of ordinary skill inthe art will recognize that this time will vary depending on thetemperature of the furnace and the quantity of MEE′XX′ or MEXX′X″X′″precursor. After melting, the furnace is turned off. The containerevenly cools to room temperature inside the insulated furnace. One ofordinary skill in the art will recognize that the amount of time to coolthe container will also depend upon the quantity of MEE′XX′ orMEXX′X″X′″ precursor.

The resulting high density materials have a density ranging fromapproximately 1.0 to the reported crystal density at room temperatureand atmospheric pressure, preferably from approximately 1.9 g/mL to thereported crystal density. The high density materials are less likely tobecome entrained in the vapor phase. Additionally, the high densitymaterials are more compact and less likely to be disturbed after packingin the sublimator. Finally, the high density material results in alarger volume in each sublimator and less separate sublimator canistersfor the customer.

Alternatively, the process described in the flowchart of FIG. 2 may beused to overcome the issues discussed above regarding vapor depositionusing solid precursors. More specifically, the low density MEE′XX′ orMEXX′X″X′″ precursors may be converted to high density adducts byreacting the MEE′XX′ or MEXX′X″X′″ precursors with a coordinatingligand. The resulting adducts have the formula MEE′XX′.L_(n) orMEXX′X″X′″.L, disclosed above. As shown in more detail in the examplesthat follow, 1 molar equivalent of the low density MEE′XX′ or MEXX′X″X′″precursor is reacted with 0.1 or more molar equivalents of ligand L withor without a solvent at a temperature ranging from approximately −50° C.to approximately 100° C. Suitable solvents include hydrocarbons,halogenated hydrocarbons, ethers, nitriles, ketones, or combinationsthereof. The order of addition is not important. In other words, the lowdensity MEE′XX′ or MEXX′X″X′″ precursors may be added to the ligand L orthe ligand L may be added to the MEE′XX′ or MEXX′X″X′″ precursor. Thecombination is maintained for approximately 0.1 hours to approximately48 hours with or without stirring. One of ordinary skill in the art willrecognize the equipment needed to perform the mixing process.

As discussed above, MoO₂Cl₂ is very difficult to handle. For large scaleprocesses, it may be beneficial to utilize a tetrahydrofuran (THF)adduct/solvent to produce a liquid solution of MoO₂Cl₂.THF₂. The THFadduct may then be replaced by the desired adduct. The replacementadduct must be more coordinating than the THF adduct in order to besuitable for replacement. For example, the nitriles may not besuccessful in this synthesis method for MoO₂Cl₂.L_(n) because it willnot displace THF. Applicants believe that chelating adducts, such asamides, diamides, esters, or anhydrides, may be suitable to displace THFusing this synthesis method.

The resulting high density adducts have a density ranging fromapproximately 1.5 g/mL to approximately 4.0 g/mL at room temperature andatmospheric pressure. Some of the resulting high density adducts mayeven be in liquid form at room temperature and atmospheric pressure. Asdiscussed above, liquid precursors are more suitable than solidprecursors for commercial vapor deposition techniques. For example,canisters of liquid precursors may be easily filled using liquidtransfer techniques. The high density adducts are less likely to becomeentrained in the vapor phase. Additionally, the high density adducts aremore compact and less likely to be jostled after packing in thesublimator. Finally, the higher density precursors are easier to handlethan lower density precursor and may permit an increased load pervolume.

Applicants expect that the M-L bonds will break at the depositiontemperature, As a result, no film contamination is expected frominclusion of the adduct in the MEE′XX′.L_(n) or MEXX′X″X′″.L precursors.As such, these precursors should behave as MEE′XX′ or MEXX′X″X′″, but beeasier to handle and use owing to their lower melting point. Thedisclosed MEE′XX′.L_(n) or MEXX′X″X′″.L precursors may also be betterthan MEE′XX′ or MEXX′X″X′″ due to a lower deposition temperature andreduced etching effect due to any deposition by-products.

Finally, Applicants believe that the disclosed MEE′XX′.L_(n) orMEXX′X″X′″.L precursors may be more stable and less hydrolysable thanthe MEE′XX′ or MEXX′X″X′″ precursors. The disclosed MEE′XX′.L_(n) orMEXX′X″X′″.L precursors may also exhibit less etching damage to thesubstrate and reactor than the MEE′XX′ or MEXX′XX″X′″ precursors. Thismay be demonstrated by comparative deposition testing. Moreparticularly, a thicker combination of the substrate and deposited filmfrom the adducted precursors as compared to the non-adducted analogs maydemonstrate reduced etching damage. Applicants believe that the adductedprecursors may increase the thickness of the substrate and depositedfilm by approximately 0% to approximately 25% as compared to thenon-adducted analogs.

In another alternative, the process disclosed in the flowchart of FIG. 3may be used to overcome the issues discussed above regarding vapordeposition using solid precursors. More particularly, the low densityMEE′XX′ or MEXX′X″X′″ precursors may be converted to low density adductsand the low density adducts converted to high density adducts byfollowing the processes in the flow chart of FIG. 2 prior to performingthe processes in the flow chart of FIG. 1. Applicants have discoveredthat several of the MEE′XX′ .L_(n) or MEXX′X″X′″.L precursors, such asL=THF or isovaleronitrile, are solids that exhibit low bulk density(e.g., ranging from approximately 0.3 to approximately 1.5 g/mL andtypically from approximately 0.6 to approximately 1.1 g/mL). As aresult, the combination of the flow charts of FIGS. 1 and 2 may providehigh density materials having a density ranging from approximately 1.0g/mL to the reported crystal density at room temperature and atmosphericpressure, preferably from approximately 1.9 g/mL to the reported crystaldensity. The high density materials are less likely to become entrainedin the vapor phase. Additionally, the high density materials are morecompact and less likely to be disturbed after packing in the sublimator.Finally, the high density material results in a larger volume in eachsublimator and less separate sublimator canisters for the customer.

In another alternative, the process disclosed in the flowchart of FIG. 4may be used to overcome the issues discussed above regarding vapordeposition using solid precursors. More particularly, the low densityMEE′XX′ or MEXX′X″X′″ precursors may be mixed with an unreactive andnon-volatile liquid to form a slurry. Approximately 1% w/w toapproximately 99% w/w of the low density MEE′XX′ or MEXX′X″X′″ precursoris added to the unreactive and non-volatile liquid at a temperatureranging from approximately −80° C. to approximately 250° C., preferablyfrom approximately −50° C. to approximately 100° C., more preferablyfrom approximately room temperature to approximately 50° C. The order ofaddition is not important. In other words, the low density MEE′XX′ orMEXX′X″X′″ precursors may be added to the unreactive and non-volatileliquid or the unreactive and non-volatile liquid may be added to the lowdensity MEE′XX′, or MEXX′X″X′″ precursor. Exemplary unreactive andnon-volatile liquids preferably have boiling points above 200° C. andexhibit a vapor pressure that is 0% to approximately 1% of the vaporpressure of the precursor. Exemplary unreactive and non-volatile liquidsinclude silicone oils, hydrocarbons, perfluorinated polyethers, andcombinations thereof. The combination is maintained with or withoutstirring until homogenous. Typically, the combination is maintainedbetween approximately 0.1 hours to approximately 48 hours, and morepreferably from approximately 0.5 hours to approximately 8 hours. One ofordinary skill in the art will recognize the equipment needed to performthe mixing process. One of ordinary skill in the art will furtherrecognize that mixing time will depend on the size of the batch and thathomogeneity will take longer for non-stirred mixtures than for stirredmixtures.

The slurries permit easier filling of and more efficient heat transferthrough the canister. The slurries are less likely to become entrainedin the vapor phase. Additionally, the slurries are more compact and lesslikely to be jostled after packing in the sublimator.

In another alternative, the flowchart of FIG. 5 may be used to overcomethe issues discussed above regarding vapor deposition using solidprecursors. More particularly, the low density MEE′XX′ or MEXX′X″X′″precursors may be mixed with an inert volatile liquid to form asolid-liquid slurry. The slurry may be transferred to the sublimator andthe volatile liquid removed to form a solid cake of the high densityMEE′XX′ or MEXX′X″X′″ precursor. Approximately 1% w/w to approximately75% why of the low density MEE′XX′ or MEXX′X″X′″ precursor is added tothe inert volatile liquid at a temperature ranging from approximately−50° C. to approximately 100° C. The order of addition is not important.In other words, the low density MEE′XX′ or MEXX′X″X′″ precursors may beadded to the inert volatile liquid or the inert volatile liquid may beadded to the low density MEE′XX′, or MEXX′X″X′″ precursor. Exemplaryinert volatile liquids include alkanes, such as pentane, hexane, orcyclohexane, or chlorinated solvents, such as SiCl₄, DCM or chloroform.The combination is maintained with or without stirring until homogenous.Typically, the combination is maintained between approximately X hoursto approximately 48 hours, and more preferably from approximately Xhours to approximately 8 hours. One of ordinary skill in the art willrecognize the equipment needed to perform the mixing process. One ofordinary skill in the art will further recognize that mixing time willdepend on the size of the batch and that homogeneity will take longerfor non-stirred mixtures than for stirred mixtures.

The resulting high density materials have a density ranging fromapproximately 1.0 g/mL to the reported crystal density at roomtemperature and atmospheric pressure. The high density materials areless likely to become entrained in the vapor phase. Additionally, thehigh density materials are more compact and less likely to be jostledafter packing in the sublimator.

Applicants believe that the disclosed Group 6 transitionmetal-containing film forming compositions treated by the processes ofFIGS. 1-5 may be suitable for use in commercial vapor depositionprocesses. More particularly, the resulting Group 6 transitionmetal-containing film forming compositions may have higher volatilityand lower melting points than the analogous non-treated composition. Asshown in the examples that follow, the proposed treatments may convertsome of the pretreated compounds into a liquid, which is morecommercially viable than solids for vapor deposition processes. Thetreatments may also increase the stability of the Group 6 transitionmetal-containing film forming compositions and/or increase thecompositions reactivity to any vapor deposition reactants as compared tothe non-treated analog. The treatments may also reduce etching of anyhalide-sensitive substrates during the vapor deposition process. Theadducts may also permit improved area selective deposition.

Methods of purifying the MEE′XX′ or MEXX′X″X′″ precursors are alsodisclosed. Any of the coordinating ligands disclosed above reacts withthe MEE′XX′ or MEXX′X″X′″ precursors to form an adduct of the generalformula MEE′XX′.L_(n) or MEXX′X″X′″.L with M=Mo, E=O, S; X═Cl, Br, I;n=1, 2. The adduct is heated to moderate temperatures (ranging fromapproximately 50° C. to approximately 300° C.) in a sublimation ordistillation process to produce a purified adduct. Subsequent treatmentof the purified adduct reverts the coordination process leading to apurified MEE′XX′ or MEXX′X″X′″. Exemplary subsequent treatments includehigh temperature (ranging from approximately 300° C. to approximately500° C., pH change, low pressure (ranging from approximately 0 toapproximately 1 Torr), ligand oxidation, photochemical, orelectrochemical. Applicants believe the purified MEE′XX′ or MEXX′X″X′″will contain less impurities than the starting MEE′XX′ or MEXX′X″X′″

Any of the disclosed Group 6 transition metal-containing film formingcompositions may exhibit (i) sufficient volatility to provide a rapidand reproducible delivery into the reaction chamber from the vessel inwhich they are stored, (ii) high thermal stability to avoiddecomposition during the storage in the canister and to enableself-limiting growth in ALD mode at high temperature, typically >150° C.for dielectric films and >275° C. for conductive films, (iii)appropriate reactivity toward the substrate terminal functions and withthe reacting gas to an easy conversion into the desired film, and (iv)high purity to obtain a film with low impurities.

Purity of the disclosed Group 6 transition metal-containing film formingcompositions is preferably higher than 99.9% w/w. The disclosed Group 6transition metal-containing film forming compositions may contain any ofthe following impurities: Mo(═NR)Cl(OR), wherein R is defined as above,alkylamines, dialkylamines, alkylimines, alkoxies, THF, ether, toluene,chlorinated metal compounds, lithium or sodium alkoxy, or lithium orsodium amide. Preferably, the total quantity of these impurities isbelow 0.1% w/w. The purified product may be produced by sublimation,distillation, and/or passing the gas or liquid through a suitableadsorbent, such as a 4A molecular sieve. For example The MEE′XX′.L_(n)or MEXX′X″X′″.L precursors may be purified by heating to a temperatureranging from approximately 75° C. to approximately 300° C., preferablyfrom approximately 100° C. to approximately 200° C., at a pressureranging from approximately 1 mTorr to approximately 500 Torr, preferablyfrom 1 Torr to 200 Torr.

The disclosed Group 6 transition metal-containing film formingcompositions may also include metal impurities at the ppbw (part perbillion weight) level. These metal impurities include, but are notlimited to, Aluminum (Al), Arsenic (As), Barium (Ba), Beryllium (Be),Bismuth (Bi), Cadmium (Cd), Calcium (Ca), Chromium (Cr), Cobalt (Co),Copper (Cu), Gallium (Ga), Germanium (Ge), Hafnium (Hf), Zirconium (Zr),Indium (In), Iron (Fe), Lead (Pb), Lithium (Li), Magnesium (Mg),Manganese (Mn), Tungsten (W), Nickel (Ni), Potassium (K), Sodium (Na),Strontium (Sr), Thorium (Th), Tin (Sn), Titanium (Ti), Tungsten (W),Uranium (U), Vanadium (V), and Zinc (Zn). The Group 6 transitionmetal-containing film forming compositions comprise betweenapproximately 0 ppb and approximately 10,000 ppb, preferably betweenapproximately 0 ppb and approximately 1,000 ppb, and more preferablybetween approximately 0 ppb and approximately 500 ppb of any one ofthese metal impurities.

Also disclosed are methods for forming Group 6 transitionmetal-containing layers on a substrate using a vapor deposition process.The method may be useful in the manufacture of semiconductor,photovoltaic, LCD-TFT, or flat panel type devices. The disclosed Group 6transition metal-containing film forming compositions may be used todeposit thin Group 6 transition metal-containing films using any vapordeposition methods known to those of skill in the art, such as AtomicLayer Deposition or Chemical Vapor Deposition. Exemplary CVD methodsinclude thermal CVD, plasma enhanced CVD (PECVD), pulsed CVD (PCVD), lowpressure CVD (LPCVD), sub-atmospheric CVD (SACVD) or atmosphericpressure CVD (APCVD), hot-wire CVD (HWCVD, also known as cat-CVD, inwhich a hot wire serves as an energy source for the deposition process),radicals incorporated CVD, and combinations thereof. Exemplary ALDmethods include thermal ALD, plasma enhanced ALD (PEALD), spatialisolation ALD, hot-wire ALD (HWALD), radicals incorporated ALD, andcombinations thereof. Super critical fluid deposition may also be used.The deposition method is preferably ALD, PE-ALD, or spatial ALD in orderto provide suitable step coverage and film thickness control.

FIG. 6 is a block diagram that schematically illustrates an example of avapor deposition apparatus that may be used to form the Group 6transition metal-containing layer. The apparatus illustrated in FIG. 6includes a reactor 11, a feed source 12 for the disclosed Group 6transition metal-containing film forming compositions, a feed source 13for reactant (typically, an oxidizing agent such as oxygen or ozone),and a feed source 14 for an inert gas that can be used as a carrier gasand/or dilution gas, A substrate loading and unloading mechanism (notshown) allows the insertion and removal of deposition substrates in thereactor 11. A heating device (not shown) is provided to reach thereaction temperatures required for reaction of the disclosedcompositions.

The Group 6 transition metal-containing film forming compositions feedsource 12 may use a bubbler method to introduce the composition into thereactor 11, and is connected to the inert gas feed source 14 by the lineL1. The line L1 is provided with a shutoff valve V1 and a flow ratecontroller, for example, a mass flow controller MFC1, downstream fromthis valve. The composition is introduced from its feed source 12through the line L2 into the reactor 11. The following are provided onthe upstream side: a pressure gauge PG1, a shutoff valve V2, and ashutoff valve V3.

The reactant feed source 13 comprises a vessel that holds the reactantin gaseous, liquid, or solid form. Vapors of the reactant are introducedfrom its feed source 13 through the line L3 into the reactor 11. Ashutoff valve V4 is provided in the line L3. This line L3 is connectedto the line L2.

The inert gas feed source 14 comprises a vessel that holds inert gas ingaseous form. The inert gas can be introduced from its feed sourcethrough the line. L4 into the reactor 11 Line L4 is provided with thefollowing on the upstream side: a shutoff valve V6, a mass flowcontroller MFC3, and a pressure gauge PG2. The line L4 joins with theline L3 upstream from the shutoff valve V4.

The line L5 branches off upstream from the shutoff valve VI in the lineL1; this line L5 joins the line L2 between the shutoff valve V2 and theshutoff valve V3. The line L5 is provided with a shutoff valve V7 and amass flow controller MFC4 considered from the upstream side.

The line L6 branches off between the shutoff valves V3 and V4 into thereaction chamber 11. This line L6 is provided with a shutoff valve S.

A line L7 that reaches to the pump PMP is provided at the bottom of thereactor 11. This line L7 contains the following on the upstream side: apressure gauge PG3, a butterfly valve BV for controlling thebackpressure, and a cold trap 15. This cold trap 15 comprises a tube(not shown) that is provided with a cooler (not shown) over itscircumference and is aimed at collecting the tungsten precursor and therelated by-products.

The reactor may be any enclosure or chamber within a device in whichdeposition methods take place such as without limitation, aparallel-plate type reactor, a cold-wall type reactor, a hot-wall typereactor, a single-wafer reactor, a multi-wafer reactor, or other typesof deposition systems under conditions suitable to cause the compoundsto react and form the layers.

The reactor contains one or multiple substrates onto which the filmswill be deposited. A substrate is generally defined as the material onwhich a process is conducted. The substrates may be any suitablesubstrate used in semiconductor, photovoltaic, flat panel, or LCD-TFTdevice manufacturing. Examples of suitable substrates include wafers,such as silicon, silica, glass, or GaAs wafers. The wafer may have oneor more layers of differing materials deposited on it from a previousmanufacturing step. For example, the wafers may include silicon layers(crystalline, amorphous, porous, etc.), silicon oxide layers, siliconnitride layers, silicon oxy nitride layers, carbon doped silicon oxide(SiCOH) layers, or combinations thereof. Additionally, the wafers mayinclude copper layers or noble metal layers (e.g. platinum, palladium,rhodium, or gold). The wafers may include barrier layers, such asmanganese, manganese oxide, etc. Plastic layers, such aspoly(3,4-ethylenedioxythiophene)poly (styrenesulfonate) [PEDOT:PSS] mayalso be used. The layers may be planar or patterned. The disclosedprocesses may deposit the Group 6 transition metal-containing layerdirectly on the wafer or directly on one or more than one (whenpatterned layers form the substrate) of the layers on top of the wafer.Furthermore, one of ordinary skill in the art will recognize that theterms “film” or “layer” used herein refer to a thickness of somematerial laid on or spread over a surface and that the surface may be atrench or a line. Throughout the specification and claims, the wafer andany associated layers thereon are referred to as substrates, Forexample, a molybdenum oxide film may be deposited onto a TiN layer. Insubsequent processing, a zirconium oxide layer may be deposited on themolybdenum layer, a second molybdenum layer may be deposited on thezirconium oxide layer, and a TiN layer may be deposited on the secondmolybdenum layer, forming a TiN/MoO_(x)/ZrO₂/MoO_(x)/TiN stack, with xranging from 2-3 inclusively, used in DRAM capacitors.

The temperature and the pressure within the reactor are held atconditions suitable for vapor depositions. In other words, afterintroduction of the vaporized composition into the chamber, conditionswithin the chamber are such that at least part of the vaporizedprecursor is deposited onto the substrate to form a Group 6 transitionmetal-containing film. For instance, the pressure in the reactor may beheld between about 1 Pa and about 10⁵ Pa, more preferably between about25 Pa and about 10³ Pa, as required per the deposition parameters.Likewise, the temperature in the reactor may be held between about 100°C. and about 500° C., preferably between about 150° C. and about 400° C.One of ordinary skill in the art will recognize that “at least part ofthe vaporized precursor is deposited” means that some or all of theprecursor reacts with or adheres to the substrate.

The temperature of the reactor may be controlled by either controllingthe temperature of the substrate holder or controlling the temperatureof the reactor wall. Devices used to heat the substrate are known in theart. The reactor wall is heated to a sufficient temperature to obtainthe desired film at a sufficient growth rate and with desired physicalstate and composition. A non-limiting exemplary temperature range towhich the reactor wall may be heated includes from approximately 100° C.to approximately 500° C. When a plasma deposition process is utilized,the deposition temperature may range from approximately 150° C. toapproximately 400° C. Alternatively, when a thermal process isperformed, the deposition temperature may range from approximately 200°C. to approximately 500° C.

The disclosed Group 6 transition metal-containing film formingcompositions may be supplied either in neat form or in a blend with asuitable solvent, such as ethyl benzene, xylene, mesitylene, decane,dodecane. The disclosed compositions may be present in varyingconcentrations in the solvent.

The neat or blended Group 6 transition metal-containing film formingcompositions are introduced into a reactor in vapor form by conventionalmeans, such as tubing and/or flow meters. The compound in vapor form maybe produced by vaporizing the neat or blended compound solution througha conventional vaporization step such as direct vaporization,distillation, or by bubbling, or by using a sublimator such as the onedisclosed in PCT Publication WO2009/087609 to Xu et al. The neat orblended composition may be fed in liquid state to a vaporizer where itis vaporized before it is introduced into the reactor. Alternatively,the neat or blended composition may be vaporized by passing a carriergas into a container containing the composition or by bubbling thecarrier gas into the composition. The carrier gas may include, but isnot limited to, Ar, He, N₂, and mixtures thereof. Bubbling with acarrier gas may also remove any dissolved oxygen present in the neat orblended composition. The carrier gas and composition are then introducedinto the reactor as a vapor.

If necessary, the container of disclosed compositions may be heated to atemperature that permits the composition to be in its liquid phase andto have a sufficient vapor pressure. The container may be maintained attemperatures in the range of, for example, approximately 0° C. toapproximately 150° C. Those skilled in the art recognize that thetemperature of the container may be adjusted in a known manner tocontrol the amount of composition vaporized.

The Group 6 transition metal-containing film forming compositions may bedelivered to a semiconductor processing tool by the disclosed Group 6transition metal-containing film forming composition delivery devices.FIGS. 28 and 29 show two embodiments of the disclosed delivery devices1.

FIG. 28 is a side view of one embodiment of the Group 6 transitionmetal-containing film forming composition delivery device 1. In FIG. 28,the disclosed Group 6 transition metal-containing film formingcomposition 11 is contained within a container 2 having at least twoconduits, an inlet conduit 3 and an outlet conduit 4. One of ordinaryskill in the precursor art will recognize that the container 2, inletconduit 3, and outlet conduit 4 are manufactured to prevent the escapeof the gaseous form of the Group 6 transition metal-containing filmforming composition 11, even at elevated temperature and pressure.

Suitable valves include spring-loaded or tied diaphragm valves. Thevalve may further comprise a restrictive flow orifice (RFO). Thedelivery device 1 should be connected to a gas manifold and in anenclosure. The gas manifold should permit the safe evacuation andpurging of the piping that may be exposed to air when the deliverydevice 1 is replaced so that any residual amount of the material doesnot react.

The delivery device 1 must be leak tight and be equipped with valvesthat do not permit escape of even minute amounts of the material whenclosed. The delivery device 1 fluidly connects to other components ofthe semiconductor processing tool, such as the gas cabinet disclosedabove, via valves 6 and 7. Preferably, the container 2, inlet conduit 3,valve 6, outlet conduit 4, and valve 7 are typically made of 316L EPstainless steel.

In FIG. 28, the end 8 of inlet conduit 3 is located above the surface ofthe Group 6 transition metal-containing film forming composition 11,whereas the end 9 of the outlet conduit 4 is located below the surfaceof the Group 6 transition metal-containing film forming composition 11.In this embodiment, the Group 6 transition metal-containing film formingcomposition 11 is preferably in liquid form. An inert gas, including butnot limited to nitrogen, argon, helium, and mixtures thereof, may beintroduced into the inlet conduit 3. The inert gas pressurizes thecontainer 2 so that the liquid Group 6 transition metal-containing filmforming composition 11 is forced through the outlet conduit 4 and tocomponents in the semiconductor processing tool (not shown). Thesemiconductor processing tool may include a vaporizer which transformsthe liquid Group 6 transition metal-containing film forming composition11 into a vapor, with or without the use of a carrier gas such ashelium, argon, nitrogen or mixtures thereof, in order to deliver thevapor to a chamber where a wafer to be repaired is located and treatmentoccurs in the vapor phase. Alternatively, the liquid Group 6 transitionmetal-containing film forming composition 11 may be delivered directlyto the wafer surface as a jet or aerosol.

FIG. 29 is a side view of a second embodiment of the Group 6 transitionmetal-containing film forming composition delivery device 1. In FIG. 29,the end 8 of inlet conduit 3 is located below the surface of the Group 6transition metal-containing film forming composition 11, whereas the end9 of the outlet conduit 4 is located above the surface of the Group 6transition metal-containing film forming composition 11. FIG. 29 alsoincludes an optional heating element 14, which may increase thetemperature of the Group 6 transition metal-containing film formingcomposition 11. The Group 6 transition metal-containing film formingcomposition 11 may be in solid or liquid form. An inert gas, includingbut not limited to nitrogen, argon, helium, and mixtures thereof, isintroduced into the inlet conduit 3. The inert gas flows through theGroup 6 transition metal-containing film forming composition 11 andcarries a mixture of the inert gas and vaporized Group 6 transitionmetal-containing film forming composition 11 to the outlet conduit 4 andto the components in the semiconductor processing tool.

Both FIGS. 28 and 29 include valves 6 and 7. One of ordinary skill inthe art will recognize that valves 6 and 7 may be placed in an open orclosed position to allow flow through conduits 3 and 4, respectively. Inanother alternative, the inlet conduit 3 and outlet conduit 4 may bothbe located above the surface of the Group 6 transition metal-containingfilm forming composition 11 without departing from the disclosureherein. Furthermore, inlet conduit 3 may be a filling port.

In another alternative, either delivery device 1 in FIG. 28 or 29, or asimpler delivery device having a single conduit terminating above thesurface of any solid or liquid present, may be used if the Group 6transition metal-containing film forming composition 11 is in vapor formor if sufficient vapor pressure is present above the solid/liquid phase.In this case, the Group 6 transition metal-containing film formingcomposition 11 is delivered in vapor form through the conduit 3 or 4simply by opening the valve 6 in FIG. 28 or 7 in FIG. 29, respectively.The delivery device 1 may be maintained at a suitable temperature toprovide sufficient vapor pressure for the Group 6 transitionmetal-containing film forming composition 11 to be delivered in vaporform, for example by the use of an optional heating element 14.

When the Group 6 transition metal-containing film forming compositionsare solids, their vapors may be delivered to the reactor using asublimator. FIG. 30 shows one embodiment of a suitable sublimator 100.The sublimator 100 comprises a container 33. Container 33 may be acylindrical container, or alternatively, may be any shape, withoutlimitation. The container 33 is constructed of materials such asstainless steel, nickel and its alloys, quartz, glass, and otherchemically compatible materials, without limitation. In certaininstances, the container 33 is constructed of another metal or metalalloy, without limitation. In certain instances, the container 33 has aninternal diameter from about 8 centimeters to about 55 centimeters and,alternatively, an internal diameter from about 8 centimeters to about 30centimeters. As understood by one skilled in the art, alternateconfigurations may have different dimensions.

Container 33 comprises a sealable top 15, sealing member 18, and gasket20. Sealable top 15 is configured to seal container 33 from the outerenvironment. Sealable top 15 is configured to allow access to thecontainer 33. Additionally, sealable top 15 is configured for passage ofconduits into container 33. Alternatively, sealable top 15 is configuredto permit fluid flow into container 33. Sealable top 15 is configured toreceive and pass through a conduit comprising a dip tube 92 to remain influid contact with container 33. Dip tube 92 having a control valve 90and a fitting 95 is configured for flowing carrier gas into container33. In certain instances, dip tube 92 extends down the center axis ofcontainer 33. Further, sealable top 15 is configured to receive and passthrough a conduit comprising outlet tube 12. The carrier gas and vaporof the Group 6 transition metal-containing film forming composition isremoved from container 33 through the outlet tube 12. Outlet tube 12comprises a control valve 10 and fitting 5. In certain instances, outlettube 12 is fluidly coupled to a gas delivery manifold, for conductingcarrier gas from the sublimator 100 to a film deposition chamber.

Container 33 and sealable top 15 are sealed by at least two sealingmembers 18; alternatively, by at least about four sealing members. Incertain instance, sealable top 15 is sealed to container 33 by at leastabout eight sealing members 18. As understood by one skilled in the art,sealing member 18 releasably couples sealable top 15 to container 33,and forms a gas resistant seal with gasket 20. Sealing member 18 maycomprise any suitable means known to one skilled in the art for sealingcontainer 33. In certain instances, sealing member 18 comprises athumbscrew.

As illustrated in FIG. 30, container 33 further comprises at least onedisk disposed therein. The disk comprises a shelf, or horizontalsupport, for solid material. In certain embodiments, an interior disk 30is disposed annularly within the container 33, such that the disk 30includes an outer diameter or circumference that is less than the innerdiameter or circumference of the container 33, forming an opening 31. Anexterior disk 86 is disposed circumferentially within the container 33,such that the disk 86 comprises an outer diameter or circumference thatis the same, about the same, or generally coincides with the innerdiameter of the container 33. Exterior disk 86 forms an opening 87disposed at the center of the disk. A plurality of disks is disposedwithin container 33. The disks are stacked in an alternating fashion,wherein interior disks 30, 34, 36, 44 are vertically stacked within thecontainer with alternating exterior disks 62, 78, 82, 86. Inembodiments, interior disks 30, 34, 36, 44 extend annularly outward, andexterior disks 62, 78, 82, 86 extend annularly toward the center ofcontainer 33. As illustrated in the embodiment of FIG. 30, interiordisks 30, 34, 36, 44 are not in physical contact with exterior disks 62,78, 82, 86.

The assembled sublimator 100 comprises interior disks 30, 34, 36, 44comprising aligned and coupled support legs 50, interior passage 51,concentric walls 40, 41, 42, and concentric slots 47, 48, 49. Theinterior disks 30, 34, 36, 44 are vertically stacked, and annularlyoriented about the dip tube 92. Additionally, the sublimator comprisesexterior disks 62, 78, 82, 86. As illustrated in FIG. 30, the exteriordisks 62, 78, 82, 86 should be tightly fit into the container 33 for agood contact for conducting heat from the container 33 to the disks 62,78, 82, 86. Preferably, the exterior disks 62, 78, 82, 86 are coupledto, or in physical contact with, the inner wall of the container 33.

As illustrated, exterior disks 62, 78, 82, 86 and interior disks 30, 34,36, 44 are stacked inside the container 33. When assembled in container33 to form sublimator 100, the interior disks 30, 34, 36, 44 form outergas passages 31, 35, 37, 45 between the assembled exterior disks 62, 78,82, 86. Further, exterior disks 62, 78, 82, 86 form inner gas passages56, 79, 83, 87 with the support legs of the interior disks 30, 34, 36,44. The walls 40, 41, 42 of interior disks 30, 34, 36, 44 form thegrooved slots for holding solid precursors. Exterior disks 62, 78, 82,86 comprise walls 68, 69, 70 for holding solid precursors. Duringassembly, the solid precursors are loaded into the annular slots 47, 48,49 of interior disks 30, 34, 36, 44 and annular slots 64, 65, 66 ofexterior disks 62, 78, 82, 86.

While FIG. 30 discloses one embodiment of a sublimator capable ofdelivering the vapor of any solid Group 6 transition metal-containingfilm forming composition to the reactor, one of ordinary skill in theart will recognize that other sublimator designs may also be suitable,without departing from the teachings herein. Finally, one of ordinaryskill in the art will recognize that the disclosed Group 6 transitionmetal-containing film forming composition 11 may be delivered tosemiconductor processing tools using other delivery devices, such as theampoules disclosed in WO 2006/059187 to Jurcik et al., without departingfrom the teachings herein.

In addition to the disclosed compositions, a reactant may also beintroduced into the reactor. The reactant may be an oxidizing gas suchas one of O₂, O₃, H₂O, H₂O₂, NO, N₂O, NO₂, oxygen containing radicalssuch as O. or OH., NO, NO₂, carboxylic acids, formic acid, acetic acid,propionic acid, and mixtures thereof. Preferably, the oxidizing gas isselected from the group consisting of O₂, O₃, H₂O, H₂O₂, oxygencontaining radicals thereof such as O. or OH., and mixtures thereof.

Alternatively, the reactant may be a reducing gas such as one of H₂,H₂CO, NH₃, SiH₄, Si₂H₆, Si₃H₈, (CH₃)₂SiH₂, (C₂H₅)₂SiH₂, (CH₃)SiH₃,(C₂H₅)SiH₃, phenyl silane, N₂H₄, N(SiH₃)₃, N(CH₃)H₂, N(C₂H₅)H₂,N(CH₃)₂H, N(C₂H₅)₂H, N(CH₃)₃, N(C₂H₅)₃, (SiMe₃)₂NH, (CH₃)HNNH₂,(CH₃)₂NNH₂, phenyl hydrazine, H₂N—C₂H₄—NH₂, substituted ethylenediamine, N-containing molecules, B₂H₆, 9-borabicyclo[3,3,1]nonane,dihydrobenzenfuran, pyrazoline, trimethylaluminium, dimethylzinc,diethylzinc, radical species thereof, and mixtures thereof. Preferably,the reducing gas is H₂, NH₃, SiH₄, Si₂H₆, Si₃H₈, SiH₂Me₂, SiH₂Et₂,N(SiH₃)₃, H₂N—C₂H₄—NH₂, hydrogen radicals thereof, or mixtures thereof.More preferably, the reducing gas is H₂N—C₂H₄—NH₂.

The reactant may be treated by a plasma, in order to decompose thereactant into its radical form. N₂ may also be utilized as a reducinggas when treated with plasma. For instance, the plasma may be generatedwith a power ranging from about 50 W to about 500 W, preferably fromabout 100 W to about 400 W. The plasma may be generated or presentwithin the reactor itself. Alternatively, the plasma may generally be ata location removed from the reactor, for instance, in a remotely locatedplasma system. One of skill in the art will recognize methods andapparatus suitable for such plasma treatment.

For example, the reactant may be introduced into a direct plasmareactor, which generates plasma in the reaction chamber, to produce theplasma-treated reactant in the reaction chamber. Exemplary direct plasmareactors include the Titan™ PECVD System produced by Trion Technologies.The reactant may be introduced and held in the reaction chamber prior toplasma processing. Alternatively, the plasma processing may occursimultaneously with the introduction of the reactant. In-situ plasma istypically a 13.56 MHz RF inductively coupled plasma that is generatedbetween the showerhead and the substrate holder. The substrate or theshowerhead may be the powered electrode depending on whether positiveion impact occurs. Typical applied powers in in-situ plasma generatorsare from approximately 30 W to approximately 1000 W. Preferably, powersfrom approximately 30 W to approximately 600 W are used in the disclosedmethods. More preferably, the powers range from approximately 100 W toapproximately 500 W. The disassociation of the reactant using in-situplasma is typically less than achieved using a remote plasma source forthe same power input and is therefore not as efficient in reactantdisassociation as a remote plasma system, which may be beneficial forthe deposition of Group 6 transition metal-containing films onsubstrates easily damaged by plasma.

Alternatively, the plasma-treated reactant may be produced outside ofthe reaction chamber. The MKS Instruments' ASTRONi® reactive gasgenerator may be used to treat the reactant prior to passage into thereaction chamber. Operated at 2.45 GHz, 7kW plasma power, and a pressureranging from approximately 0.5 Torr to approximately 10 Torr, thereactant O₂ may be decomposed into two O radicals, Preferably, theremote plasma may be generated with a power ranging from about 1 kW toabout 10 kW, more preferably from about 2.5 kW to about 7.5 kW.

The vapor deposition conditions within the chamber allow the disclosedcomposition and the reactant to react and form a Group 6 transitionmetal-containing film on the substrate. In some embodiments, Applicantsbelieve that plasma-treating the reactant may provide the reactant withthe energy needed to react with the disclosed precursors.

Depending on what type of film is desired to be deposited, an additionalprecursor may be introduced into the reactor. The precursor may be usedto provide additional elements to the Group 6 transitionmetal-containing film. The additional elements may include lanthanides(Ytterbium, Erbium, Dysprosium, Gadolinium, Praseodymium, Cerium,Lanthanum, Yttrium), zirconium, germanium, silicon, titanium, manganese,ruthenium, bismuth, lead, magnesium, aluminum, or mixtures of these.When an additional precursor compound is utilized, the resultant filmdeposited on the substrate contains the Group 6 transition metal incombination with at least one additional element.

The Group 6 transition metal-containing film forming compositions andreactants may be introduced into the reactor either simultaneously(chemical vapor deposition), sequentially (atomic layer deposition) ordifferent combinations thereof. The reactor may be purged with an inertgas between the introduction of the composition and the introduction ofthe reactant. Alternatively, the reactant and the composition may bemixed together to form a reactant/composition mixture, and thenintroduced to the reactor in mixture form. Another example is tointroduce the reactant continuously and to introduce the Group 6transition metal-containing film forming compositions by pulse (pulsedchemical vapor deposition).

The vaporized composition and the reactant may be pulsed sequentially orsimultaneously (e.g. pulsed CVD) into the reactor. Each pulse may lastfor a time period ranging from about 0.01 seconds to about 10 seconds,alternatively from about 0.3 seconds to about 3 seconds, alternativelyfrom about 0.5 seconds to about 2 seconds. In another embodiment, thereactant may also be pulsed into the reactor. In such embodiments, thepulse of each gas may last for a time period ranging from about 0.01seconds to about 10 seconds, alternatively from about 0.3 seconds toabout 3 seconds, alternatively from about 0.5 seconds to about 2seconds. In another alternative, the vaporized compositions andreactants may be simultaneously sprayed from a shower head under which asusceptor holding several wafers is spun (spatial ALD).

Depending on the particular process parameters, deposition may takeplace for a varying length of time. Generally, deposition may be allowedto continue as long as desired or necessary to produce a film with thenecessary properties. Typical film thicknesses may vary from severalangstroms to several hundreds of microns, depending on the specificdeposition process. The deposition process may also be performed as manytimes as necessary to obtain the desired film.

In one non-limiting exemplary CVD type process, the vapor phase of thedisclosed Group 6 transition metal-containing film forming compositionsand a reactant are simultaneously introduced into the reactor. The tworeact to form the resulting Group 6 transition metal-containing thinfilm. When the reactant in this exemplary CVD process is treated with aplasma, the exemplary CVD process becomes an exemplary PECVD process.The reactant may be treated with plasma prior or subsequent tointroduction into the chamber.

In a second non-limiting exemplary CVD type process, the vapor phase ofone of the disclosed Group 6 transition metal-containing film formingcompositions, for example MoO₂Cl₂.EDA, is introduced into the reactorset at a temperature ranging from approximately 250° C. to approximately350° C. No reactant is introduced, Alternatively, additional EDA may beused as a reducing agent. The EDA reacts with the MoO₂Cl₂ to produce ashiny, highly conductive, metallic Mo-containing film. Analysis isongoing, but Applicants believe that the Mo-containing film is Mo, MoC,MoN, or MoCN.

A third non-limiting exemplary CVD type process using the vapor phase ofone of the Group 6 transition metal-containing film forming compositionscomprising a liquid Mo adducted precursor MoO₂Cl₂.L_(n), such asMoO₂Cl₂.(methyl hexanoate)₂ is also disclosed. A shower head reactorinto which a substrate (e.g. Si wafer) was loaded and either maintainedat room temperature or heated to a temperature ranging up to 1000° C.,preferably from approximately 100° C. to approximately 700° C., morepreferably from approximately 250° C. to approximately 700° C. Whileheating occurred, the reaction chamber was purged with a flow ofnitrogen which was introduced through a port. The reactor chamber wassubsequently depressurized to about 10 torr.

After reaching the set temperature, the reaction chamber and substrate(e.g. Si wafer) were allowed to reach thermal equilibrium over a periodof approximately 30 minutes. The reactor pressure was then adjusted toabout 1 torr.

Hydrogen gas, used as a coreactant, was then introduce into the reactora flow rate ranging from approximately 1 sccm to approximately 10,000sccm, preferably from approximately 10 sccm to approximately 1,000 sccm.

When pressure reached an equilibrium, a valve between the canistercharged with MoO₂Cl₂.L liquid adduct was opened and vapors of adductedmolecule were delivered into the reactor chamber causing a metal filmdeposited on the substrate (e.g. Si wafer). Argon carrier gas used.

After deposition time was ended, the chamber is re-pressurized withnitrogen to atmospheric pressure while maintaining temperature. Thedeposited substrate (e.g. Si wafer) is removed to a nitrogen saturatedchamber for cooling to ambient temperature. The thickness of thedeposited metal film on the wafer is measured by SEM. The composition ofthe metal film is checked by XPS and/or EDX.

In one non-limiting exemplary ALD type process, the vapor phase of thedisclosed Group 6 transition metal-containing film forming compositionsis introduced into the reactor, where it is contacted with a suitablesubstrate. Excess composition may then be removed from the reactor bypurging and/or evacuating the reactor. A desired gas (for example, H₂)is introduced into the reactor where it reacts with the adsorbedcomposition in a self-limiting manner. Any excess reducing gas isremoved from the reactor by purging and/or evacuating the reactor. Ifthe desired film is a Group 6 transition metal-containing film, thistwo-step process may provide the desired film thickness or may berepeated until a film having the necessary thickness has been obtained.

Alternatively, if the desired film contains Group 6 transition metal anda second element, the two-step process above may be followed byintroduction of the vapor of an additional precursor into the reactor.The additional precursor will be selected based on the nature of theGroup 6 transition metal film being deposited. After introduction intothe reactor, the additional precursor is contacted with the substrate.Any excess precursor is removed from the reactor by purging and/orevacuating the reactor. Once again, a desired gas may be introduced intothe reactor to react with the adsorbed precursor. Excess gas is removedfrom the reactor by purging and/or evacuating the reactor. If a desiredfilm thickness has been achieved, the process may be terminated.However, if a thicker film is desired, the entire four-step process maybe repeated. By alternating the provision of the Group 6 transitionmetal-containing film forming compositions, additional precursor, andreactant, a film of desired composition and thickness can be deposited.

When the reactant in this exemplary ALD process is treated with aplasma, the exemplary ALD process becomes an exemplary PEALD process.The reactant may be treated with plasma prior or subsequent tointroduction into the chamber.

In a second non-limiting exemplary ALD type process, the vapor phase ofone of the disclosed Group 6 transition metal-containing film formingcompositions, for example MoO₂Cl₂, is introduced into the reactor, whereit is contacted with a TiN substrate. Excess composition may then beremoved from the reactor by purging and/or evacuating the reactor. Adesired gas (for example, O₃) is introduced into the reactor where itreacts with the absorbed precursor in a self-limiting manner to form amolybdenum oxide film. Any excess oxidizing gas is removed from thereactor by purging and/or evacuating the reactor. These two steps may berepeated until the molybdenum oxide film obtains a desired thickness,typically around 10 angstroms. ZrO₂ may then be deposited on the MoO_(x)film, wherein x is inclusively 2-3. For example, ZrCp(NMe₂)₃ may serveas the Zr precursor. The second non-limiting exemplary ALD processdescribed above using MoO₂Cl₂ and ozone may then be repeated on the ZrO₂layer, followed by deposition of TiN on the MoO_(x) layer. The resultingTiN/MoO_(x)/ZrO₂/MoO_(x)/TiN stack may be used in DRAM capacitors.

The Group 6 transition metal-containing films resulting from theprocesses discussed above may include a pure Group 6 transition metal(M=Mn or W), Group 6 transition metal silicide (M_(k)Si_(l)), Group 6transition metal oxide (M_(n)O_(m)), Group 6 transition metal nitride(M_(o)N_(p)) film, Group 6 transition metal carbide (M_(g)C_(r)) film,or a Group 6 transition metal carbonitride (MC_(r)N_(p)) wherein k, l,m, n, o, p, q, and r are integers which inclusively range from 1 to 6.One of ordinary skill in the art will recognize that by judicialselection of the appropriate disclosed Group 6 transitionmetal-containing film forming compositions, optional precursors, andreactants, the desired film composition may be obtained.

For example, the deposition of pure tungsten may be used to fill theholes that make contact to the transistor source and drain (“contactholes”) and also to fill vias between successive layers of metal. Thisapproach is known as a “tungsten plug” process. The usage of tungstenmay be developed due to the good properties of the films deposited usingWF₆. However, it is necessary to provide an adhesion/barrier layer suchas Ti/TiN to protect the underlying Si from attack by fluorine and toensure adhesion of tungsten to the silicon dioxide.

Alternatively, tungsten-silicide may be used on top of polysilicon gatesto increase conductivity of the gate line and thus increase transistorspeed. This approach is popular in DRAM fabrication, where the gate isalso the word line for the circuit. WF₆ and SiH₄ may be used, butdichlorosilane (SiCl₂H₂) is more commonly employed as the siliconsource, since it allows higher deposition, temperatures and thus resultsin lower fluorine concentration in the deposited film.

In another alternative,e tungsten nitride (WN_(x)) or Molybdenum nitride(MoN_(x)) are considered to be a good barrier against diffusion ofcopper in microelectronics circuits. WN_(x) and MoN_(x) may also be usedin electrodes for thin-film capacitors and field-effect transistor.

Upon obtaining a desired film thickness, the film may be subject tofurther processing, such as thermal annealing, furnace-annealing, rapidthermal annealing, UV or e-beam curing, and/or plasma gas exposure.Those skilled in the art recognize the systems and methods utilized toperform these additional processing steps. For example, the Group 6transition metal-containing film may be exposed to a temperature rangingfrom approximately 200° C. and approximately 1000° C. for a time rangingfrom approximately 0.1 second to approximately 7200 seconds under aninert atmosphere, a H-containing atmosphere, a N-containing atmosphere,an O-containing atmosphere, or combinations thereof. Most preferably,the temperature is 400° C. for 3600 seconds under a H-containingatmosphere or an O-containing atmosphere. The resulting film may containfewer impurities and therefore may have an improved density resulting inimproved leakage current. The annealing step may be performed in thesame reaction chamber in which the deposition process is performed.Alternatively, the substrate may be removed from the reaction chamber,with the annealing/flash annealing process being performed in a separateapparatus. Any of the above post-treatment methods, but especiallythermal annealing, has been found effective to reduce carbon andnitrogen contamination of the Group 6 transition metal-containing film.This in turn tends to improve the resistivity of the film.

After annealing, the tungsten-containing films deposited by any of thedisclosed processes may have a bulk resistivity at room temperature ofapproximately 5.5 μohm.cm to approximately 70 μohm.cm, preferablyapproximately 5.5 μohm.cm to approximately 20 μohm.cm, and morepreferably approximately 5.5 μohm.cm to approximately 12 μohm.cm. Afterannealing, the molybdenum-containing films deposited by any of thedisclosed processes may have a bulk resistivity at room temperature ofapproximately 50 μohm.cm to approximately 1,000 μohm.cm. Roomtemperature is approximately 20° C. to approximately 28° C. depending onthe season. Bulk resistivity is also known as volume resistivity. One ofordinary skill in the art will recognize that the bulk resistivity ismeasured at room temperature on W or Mo films that are typicallyapproximately 50 nm thick. The bulk resistivity typically increases forthinner films due to changes in the electron transport mechanism. Thebulk resistivity also increases at higher temperatures.

In another alternative, the disclosed Group 6 transitionmetal-containing film forming compositions may be used as doping orimplantation agents. Part of the disclosed composition may be depositedon top of the film to be doped, such as an indium oxide (In₂O₃) film,vanadium dioxide (VO₂) film, a titanium oxide film, a copper oxide film,or a tin dioxide (SnO₂) film. The molybdenum or tungsten then diffusesinto the film during an annealing step to form the molybdenum-dopedfilms {(Mo)In₂O₃, (Mo)VO₂, (Mo)TiO, (Mo)CuO, or (Mo)SnO₂} ortungsten-doped films {(W)In₂O₃, (W)VO₂, (W)TiO, (W)CuO, or (W)SnO₂}.See, e.g., US2008/0241575 to Lavoie et al., the doping method of whichis incorporated herein by reference in its entirety. Alternatively, highenergy ion implantation using a variable energy radio frequencyquadrupole implanter may be used to dope the molybdenum or tungsten ofthe disclosed compositions into a film. See, e.g., Kensuke et al., JVSTA16(2) March/April 1998, the implantation method of which is incorporatedherein by reference in its entirety. In another alternative, plasmadoping, pulsed plasma doping or plasma immersion ion implantation may beperformed using the disclosed compositions. See, e.g., Felch et al.,Plasma doping for the fabrication of ultra-shallow junctions SurfaceCoatings Technology, 156 (1-3) 2002, pp. 229-236, the doping method ofwhich is incorporated herein by reference in its entirety.

EXAMPLES

The following non-limiting examples are provided to further illustrateembodiments of the invention. However, the examples are not intended tobe all inclusive and are not intended to limit the scope of theinventions described herein.

Example 1 Synthesis of MoO₂Cl₂(L)_(n)

All reactions were carried out in dried glassware under an oxygen-freenitrogen atmosphere using a glove box and standard Schlenk techniques.All reagents were purchased commercially and used as received.

Inside a glove box, a 13 mL glass vial was loaded with 1 g (0.005 mol)of solid MoO₂Cl₂.An excess of the appropriate adduct was added dropwise(see Table 1 for details). Dichloromethane (DCM) was sometimes used as asolvent to promote solid-liquid mixing and to facilitate work up. One ofordinary skill in the art will recognize that other solvents may be usedin place of DCM, including, but not limited to dichloroethane,1-chlorobenzene, 2-methyltetrahydrofuran or a 3:1 mixture of ethylacetate:ethanol. The mixture was allowed to react at room temperaturefor 10 minutes to 48 hours. In small scales, the reaction typicallytakes place in approximately 5 to approximately 10 minutes. Larger scalereactions will obviously take longer. The supernatant liquid wasfiltered through a PTFE filter. The filtrate was evaporated under vacuumto remove solvent and/or excess ligand yielding the pure MoO₂Cl₂.L_(n)oil or solid.

TABLE 1 VP³ Product Adducting Ligand Ligand Product at~100 C. Formula¹Ligand CAS # Equiv² Solvent Properties (torr) MoO₂Cl₂•(tBuCN)Pivalonitrile 630-18- 3 None White ~8.1 3 crystalline solidMoO₂Cl₂•(nPrCN)₂ Butyronitrile 109-74- 5-6 None White waxy ~8.0 0 solidMoO₂Cl₂•(nC₅H₁₁C—CN)₂ Hexanenitrile 628-73- 5-6 None Pale yellow ~8.2 9solid MoO₂Cl₂•(iBuCN)₂ Iso- 625-28- 5-6 None White solid ~5.9valeronitrile 5 MoO₂Cl₂•(iPrCN)₂ Isobuty- 78-82-0 5-6 None White waxy~10.0 ronitrile solid MoO₂Cl₂•(VA) Valeric 2082- 5-6 None White solidN/A⁴ anhydride 59-9 (VA) MoO₂Cl₂•(H—C(═O)—N^(n)Bu₂)₂ N,N’-dibutyl761-65- 3 None Pale yellow ~1.7 formamide 9 oilMoO₂Cl₂•(H—C(═O)—N^(n)Et₂)₂ N,N’-diethyl 617-84- 3 DCM White solid ~0.4formamide 5 MoO₂Cl₂•(Me—C(═O)—N^(n)Et₂)₂ N,N’-diethyl 685-91- 2 NonePale green ~0.27 acetamide 6 waxy solid MoO₂Cl₂•(TPMA) N,N,N’,N’-143356- 1.5 DCM Green ~0.35 tetra 43-8 heavy oil Propylmalon amide(TPMA) MoO₂Cl₂•(CH₃C(O)C₄H₉)₂ 2-hexanone 591-78- 3 None Blue Oil ~14 at6 ~93 C. MoO₂Cl₂•(MH)₂ Methyl 106-70- 3 None Pale blue ~14 hexanoate 7oil (MH) MoO₂Cl₂•(AA)₂ Amyl acetate 628-63- 3 None Pale blue ~8.5 (AA) 7oil MoO₂Cl₂•(Et₂O)₂ Diethyl ether 115-10- 10 None Pale green ~14.5 6solid MoO₂Cl₂•(Bu₂O)₂ Dibutyl ether 142-96- 5 None Blue solid N/A⁴ 1MoO₂Cl₂•(EGBE) Ethylene 112-48- 1.1 None Blue Oil ~0.5 glycol dibutyl 1ether (EGBE) MoO₂Cl₂•(EGEE) Ethylene 629-14- 3 None White solid ~0.5glycol diethyl 1 ether (EGEE) MoO₂Cl₂•(SPr₂)₂ Dipropyl 111-47- 2 NoneGreen oil N/A⁴ sulfide 7 MoO₂Cl₂•(2-Me-cSC₄H₈)₂ (2-Methyl 1795- 2 NoneGreen oil N/A⁴ tetra 09-1 hydrothiophne MoO₂Cl₂•(SEt₂)₂ Diethyl 352-93-2 None Green oil N/A⁴ sulfide 2 ¹Except for the bulky pivalonitrile andbidentate ligands, Applicant believes that most of the adducts formMoO₂Cl₂•L₂, but testing is ongoing to confirm. ²The excess amount ofmolar equivalents of adduct added dropwise to MoO₂Cl₂. ³Vaporpressure-as calculated from TGA. ⁴N/A = Not available

FIG. 7 is a ThermoGravimetric Analysis (TGA) graph illustrating thepercentage of weight loss upon temperature increase of MoO₂Cl₂.L_(n),wherein a solid line is for L=butyronitrile, a solid short dash-dot isfor L=isovalerontrile, a solid long dash-dot is for L=isobutyronitrile,an empty dash is for L=pivalontrile, and a double empty line is forL=hexanenitrile.

FIG. 8 is a TGA graph illustrating the percentage of weight loss upontemperature increase of MoO₂Cl₂.L₂, wherein a solid line is for L=methylhexanoate, a half solid-half empty dash line is for L=amyl acetate, adotted line is for L=2-hexanone, an empty dashed line is forL=N,N-diethylformamide, and a dot-empty dash line is forN,N-dibutylformamide.

FIG. 9 is a TGA graph illustrating the percentage of weight loss upontemperature increase of MoO₂Cl₂.L₂, wherein a solid line is forL=ethylene glycol diethyl ether, a dotted line is for L=dibutyl ether, asolid dashed line is for L=diglyme, two empty dashed lines is forL=diethy ether, and a dot-solid dash line is for L=ethylene glycoldibutyl ether.

FIG. 10 is a TGA graph illustrating the percentage of weight loss upontemperature increase of MoO₂Cl₂.L₂, wherein a solid line is forL=dipropyl sulfide and a dotted line is for L=diethyl sulfide. The blanksubtract was inadvertently omitted form the TGA curve forMoO₂Cl₂.(SEt₂)₂ and, as a result, part of the curve is below the x axis.

One of ordinary skill in the art will recognize that vapour depositionis typically performed under vacuum and that the results fromatmospheric TGA are typically worse than those from vacuum TGA.

FIG. 11 is the ¹H NMR spectrum of the MoO₂Cl₂.(Methyl Hexanoate)₂precursor. FIG. 12 is the ¹H NMR spectrum of the MoO₂Cl₂.(Amyl Acetate)₂precursor.

Example 2 Synthesis of the MoO₂Cl₂(THF)₂ Intermediate [Journal of theAmerican Chemical Society, 112, 3875]

Inside a glove box, a 13 mL glass vial was loaded with 3 mL of THF at−30° C. to which 1 g of solid MoO₂Cl₂ was added in three portions. Thereaction took place instantly to form a slightly turbid colorlesssolution. The reaction product crude was filtered through a PTFE filter.The clear filtrate was evaporated under vacuum to remove excess THFyielding the pure adduct as a white crystalline solid.

FIG. 13 is a TGA/Differential Thermal Analysis (DTA) graph illustratingthe percentage of weight loss (TGA—solid line) or the differentialtemperature (DTA—dotted line) of MoO₂Cl₂.(THF)₂ upon temperatureincrease. While widely used in catalysis, FIG. 13 demonstrates that thethermal properties of the MoO₂Cl₂.(THF)₂ adduct are among the worsttested to date, with several steps indicating differingdecomposition/phase change temperatures and high residue. FIG. 13further demonstrate that this compound would not be viable in vapordeposition processes. Despite its unsatisfactory thermal properties, theMoO₂Cl₂.(THF)₂ adduct is of great synthetic utility as it can be easilyused as an intermediate to make other adducts of interest. The THFadducts are not strongly bound to the Mo, allowing “easy” replacement ofTHF with other adducts (in a two-step one-pot reaction).

Example 3 Adducts Prepared from MoO₂Cl₂(THF)₂ Intermediate

Inside a glove box, a 13 mL glass vial was loaded with 3 mL of THF at−30° C. to which 1 g of solid MoO₂Cl₂ was added in three portions. Thereaction took place instantly to form a slightly turbid colorlesssolution. An excess of the appropriate adduct was added drop wise (seeTable 2 for details). The reaction took place immediately producing acolor change. The reaction product crude was filtered through a PTFEfilter. The filtrate was evaporated under vacuum to remove excess THFand adduct yielding the pure adduct.

TABLE 2 Product Adduct Adduct Product Formula Adduct CAS # Equiv¹Properties TGA MoO₂Cl₂• Tetramethylene 110-18-9 2   Brown FIG. (TMEDA)diamine solid 14 MoO₂Cl₂• Acetylacetone 123-54-6 1.5 White None (acac)solid ¹The excess amount of molar equivalents of adduct added dropwiseto MoO₂Cl₂.

FIG. 14 is a TGA graph illustrating the percentage of weight loss ofMoO₂Cl₂.L_(n), wherein L is TMEDA and n is 1, upon temperature increase.FIG. 14 demonstrates that this compound would not be viable in vapordeposition processes due to the large amount of residue.

Example 4 Preparation of Heptyl Cyanide MoO₂Cl₂ AdductMoO₂Cl2[CH₃(CH₂)₆CN]₂

Inside a glove box, a 13 mL glass vial was loaded with 1 g of solidMoO₂Cl₂, to which 3.84 mL heptyl cyanide were added drop wise. Themixture was allowed to react at room temperature for 20 minutes. Thesupernatant liquid was filtered through a PTFE filter. The filtrate waswashed with cyclohexane (3×5 mL) to remove excess heptyl cyanide. Theresulting clear solution was evaporated under vacuum to yield the pureadduct as a pale yellow oil.

FIG. 15 is a TGA/Differential Thermal Analysis (DTA) graph illustratingthe percentage of weight loss (TGA—solid line) or the differentialtemperature (DTA—dotted line) of MoO₂Cl₂.(heptyl cyanide)₂ upontemperature increase.

This example is the same as Example 1, but it includes an additional 3washings with cyclohexane to remove the excess adduct (heptyl cyanide).This example provides an alternative way to remove adducts that may haveespecially high boiling points (heptyl cyanide 200° C. approx.). Some ofthe adducts are not too volatile, so they require long evaporation timesunder vacuum (sometimes overnight to be 100% sure), slowing the overallsynthetic procedure. This example demonstrates that a couple washings incyclohexane can remove the excess adduct, eliminating the need for longevaporation times.

Example 5 ALD of Mo(═O)₂Cl₂

ALD tests were performed using the Mo(═O)₂Cl₂, which was placed in avessel heated up to 35° C. and NH₃ as co-reactant. Typical ALDconditions were used with a reactor pressure fixed at ˜0.3 Torr. ALDbehavior with complete surface saturation and reaction were assessed ina temperature window of 300-475° C. on pure silicon wafers. FIG. 16 is agraph of the growth rates of the Mo containing film in ALD mode usingMo(═O)₂Cl₂ as a function of the temperature. Growth rate was assessed tobe 0.8 Å/cycle between 425 and 475° C. where the growth is stable withthe temperature increase. FIG. 17 is a graph of the growth rates of theMo containing film in ALD mode using the Mo(═O)₂Cl₂ as a function of theprecursor introduction time at 400° C. The flat growth rate of the ofthe Mo containing film using the Mo(═O)₂Cl₂ as a function of theprecursor introduction time demonstrate the surface self limitingproperties of the process. FIG. 18 is a graph of the growth rates of theMo containing film in ALD mode using the Mo(═O)₂Cl₂ as a function of theammonia introduction time at 400° C. FIG. 19 is a graph of the growthrates of the Mo containing film in ALD mode using the Mo(═O)₂Cl₂ as afunction of the number of ALD cycle. The linear increase of the growthrate with the number of ALD cycle is in agreement with the surface selflimiting regime characteristic of the ALD mode.

FIG. 20 to FIG. 23 is a graph of the Auger Electron Spectroscopy (AES)analysis of the films produced at 400, 425, 450 and 475° C.respectively. From 425° C. and above, films were found to be pureMolybdenum nitride. One of ordinary skill in the art will recognize thatthe same sputter rate may not have been used for each analysis.

FIG. 24 is a X-Ray Spectroscopy (XPS) graph of the MoN film produced at400° C. showing the residual amount of chlorine in the film.

FIG. 25 is a graph of the film resistivities as a function oftemperature.

FIG. 26 shows the X-Rays Diffractometry (XRD) analysis of the MoN filmproduced 475° C. showing the characteristic signals of MolybdenumNitride.

FIG. 27 is a Scanning Electron Microscope (SEM) picture of the filmdeposited in a 1:10 aspect ratio pattern wafer at 475° C. and showsnearly perfect step coverage performance.

While embodiments of this invention have been shown and described,modifications thereof can be made by one skilled in the art withoutdeparting from the spirit or teaching of this invention. The embodimentsdescribed herein are exemplary only and not limiting, Many variationsand modifications of the composition and method are possible and withinthe scope of the invention. Accordingly the scope of protection is notlimited to the embodiments described herein, but is only limited by theclaims which follow, the scope of which shall include all equivalents ofthe subject matter of the claims.

What is claimed is:
 1. A Group 6 transition metal-containing filmforming composition delivery device comprising a canister having aninlet conduit and an outlet conduit and containing the Group 6transition metal-containing film forming composition comprising aprecursor having the formula MEE′XX′ .Ln, wherein M=Mo or W; E and E′independently=O or S; X and X′ independently=Cl, Br, or I; L is anadduct; and n=1 or
 2. 2. The Group 6 transition metal-containing filmforming composition delivery device of claim 1, wherein L is ester. 3.The Group 6 transition metal-containing film forming compositiondelivery device of claim 1, wherein the precursor isMoO₂Cl₂(nC₅H₁₁—CN)₂, MoO₂Cl₂.(methyl hexanoate)₂, MoO₂Cl₂.(amylacetate)₂, or MoO₂Cl₂.(^(n)Bu-O—CH₂—CH₂—O-^(n)Bu).
 4. The Group 6transition metal-containing film forming composition delivery device ofclaim 1, wherein the Group 6 transition metal-containing film formingcomposition has a total concentration of metal impurities ranging fromapproximately 0 ppb to approximately 10,000 ppb.
 5. The Group 6transition metal-containing film forming composition delivery device ofclaim 1, wherein the Group 6 transition metal-containing film formingcomposition comprises between approximately 0% w/w and 5% w/w of anyMEE′HXHX′ by-products.
 6. A method for deposition a Group 6 transitionmetal-containing film on a substrate, the method comprising: introducinga vapor of the Group 6 transition metal-containing film formingcomposition into a reactor containing a substrate and depositing atleast part of the precursor onto the substrate to form the Group 6transition metal-containing film wherein the composition comprises aprecursor having the formula MEE′XX′.Ln, wherein M=Mo or W; E and E′independently=O or S; X and X′ independently=Cl, Br, or I; L is anadduct; and n=1 or
 2. 7. The method of claim 6, further comprisingintroducing a reactant into the reactor.
 8. The method of claim 6,wherein the Group 6 transition metal-containing film is selectivelydeposited onto the substrate.
 9. The method of claim 6, wherein L is anester.
 10. The method of claim 6, wherein the precursor isMoO₂Cl₂(nC₅H₁₁—CN)₂, MoO₂Cl₂.(methyl hexanoate)₂, MoO₂Cl₂.(amylacetate)₂, or MoO₂Cl₂.(^(n)Bu-O—CH₂—CH₂—O-^(n)Bu).